A model for estimating the potential biomagnification of chemicals in a generic food web: Preliminary development

GOAL, SCOPE AND BACKGROUND: Bioaccumulation and biomagnification of organic pollutants have been increasingly assessed and modeled during the last years. Due to the complexity of these processes and the large variability of food webs, setting generic assessments for these parameters is really difficult. Equilibrium models, based on a compound's lipophylicity, are the main tool in regulatory proposals, such as for identifying Persistent, Bioaccumulative and Toxic Substances (PBTs), although a refinement has been claimed by the scientific community. Toxicokinetic studies offer an alternative for these estimations, where biomagnification is modeled as a succession of bioaccumulation processes, each one regulated by toxicokinetic parameters. METHODS: A review of kinetic models covering species belonging to different trophic levels and with different ecological behavior has been conducted. The results were employed for setting a conceptual model for estimating the biomagnification potential in a generic food web, which was mathematically implemented through system dynamic models developed under data sheet software. Crystal Ball was then employed for allowing Monte Carlo based probabilistic calculations. Bioaccumulation laboratory assays have been performed to estimate toxicokinetic parameters in mussels (Mytilus edulis) with two PAHs (chrysene and benzo[a]pyrene). The contamination was delivered via food. The exposure period lasted more than one month followed then by a depuration phase. The contaminant content was determined on an individual basis on five replicates. RESULTS AND DISCUSSION:. The reviewed information suggested the development of a tiered conceptual biomagnification model, starting with a simplified food chain which can be refined to more realistic and complex models in successive levels. CONCLUSIONS: The mathematical implementation of the conceptual model offers tools for estimating the potential for bioaccumulation and biomagnification of chemicals under very different conditions. The versatility of the model can be used for both comparative estimations and for validating the model. RECOMMENDATIONS AND PERSPECTIVES: Since bioaccumulation and biomagnification processes are crucial elements for a proper risk assessment of chemicals, their estimation by mathematical models has been widely tested. However, inregulatory assessments, too simplistic models are still being used quite often. The biomagnification model presented in this study should be amore accurate alternative to these models. In comparison to other previously published biomagnification models, the present one covers the time variation of bioaccumulation using just a few toxicokinetic parameters.     

U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.     

Characterizing ammonia emissions from swine farms in eastern North Carolina: part 1--conventional lagoon and spray technology for waste treatment

Ammonia (NH3) fluxes from waste treatment lagoons and barns at two conventional swine farms in eastern North Carolina were measured. The waste treatment lagoon data were analyzed to elucidate the temporal (seasonal and diurnal) variability and to derive regression relationships between NH3 flux and lagoon temperature, pH and ammonium content of the lagoon, and the most relevant meteorological parameters. NH3 fluxes were measured at various sampling locations on the lagoons by a flowthrough dynamic chamber system interfaced to an environmentally controlled mobile laboratory. Two sets of open-path Fourier transform infrared (FTIR) spectrometers were also used to measure NH3 concentrations for estimating NH3 emissions from the animal housing units (barns) at the lagoon and spray technology (LST) sites. Two different types of ventilation systems were used at the two farms. Moore farm used fan ventilation, and Stokes farm used natural ventilation. The early fall and winter season intensive measurement campaigns were conducted during September 9 to October 11, 2002 (lagoon temperature ranged from 21.2 to 33.6 degrees C) and January 6 to February 2, 2003 (lagoon temperature ranged from 1.7 to 12 degrees C), respectively. Significant differences in seasonal NH3 fluxes from the waste treatment lagoons were found at both farms. Typical diurnal variation of NH3 flux with its maximum value in the afternoon was observed during both experimental periods. Exponentially increasing flux with increasing surface lagoon temperature was observed, and a linear regression relationship between logarithm of NH3 flux and lagoon surface temperature (T1) was obtained. Correlations between lagoon NH3 flux and chemical parameters, such as pH, total Kjeldahl nitrogen (TKN), and total ammoniacal nitrogen (TAN) were found to be statistically insignificant or weak. In addition to lagoon surface temperature, the difference (D) between air temperature and the lagoon surface temperature was also found to influence the NH3 flux, especially when D > 0 (i.e., air hotter than lagoon). This hot-air effect is included in the statistical-observational model obtained in this study, which was used further in the companion study (Part II), to compare the emissions from potential environmental superior technologies to evaluate the effectiveness of each technology.     

Monitoring air quality with lichens: a comparison between mapping in forest sites and in open areas

Four different methods of epiphytic lichen mapping were used for the assessment of air quality in the region under the influence of the Sostanj Thermal Power Plant (Salek Valley, Slovenia). Three methods were based on the presence of different lichen species (VDI, EU and ICP-Forest), the fourth on a frequency and coverage assessment of different growth forms of epiphytic lichens, e.g. crustose, foliose and fruticose (SI). A comparison of the results from the assessment of air quality between forest sites (ICP-Forest, SI) and open areas (VDI, EU and SI), obtained by the different methods of epiphytic lichen mapping, is presented in the contribution. Data showed that lichen species richness is worse in forest sites in comparison with open areas. From the data obtained it can be concluded that epiphytic lichen mapping in open areas is a better method for the assessment of air pollution in a given area than mapping in forest sites. The species-based methods in open areas are more powerful and useful for air quality assessment in polluted research areas than the SI and ICP-Forest methods.     

Runoff of pesticides from rice fields in the Ile de Camargue (Rhône river delta, France): field study and modeling

A field study on the runoff of pesticides was conducted during the cultivation period in 2004 on a hydraulically isolated rice farm of 120 ha surface with one central water outlet. Four pesticides were studied: Alphamethrin, MCPA, Oxadiazon, and Pretilachlor. Alphamethrin concentrations in runoff never exceeded 0.001 microg L(-1). The three other pesticides were found in concentrations between 5.2 and 28.2 microg L(-1) in the runoff water shortly after the application and decreased thereafter. The data for MCPA compared reasonably well with predictions by an analytical runoff model, accounting for volatilization, degradation, leaching to groundwater, and sorption to soil. The runoff model estimated that runoff accounted for as much as 18-42% of mass loss for MCPA. Less runoff is observed and predicted for Oxadiazon and Pretilachlor. It was concluded that runoff from rice paddies carries important loads of dissolved pesticides to the wetlands in the Ile de Camargue, and that the model can be used to predict this runoff.     

Heavy metal accumulation in Littoraria scabra along polluted and pristine mangrove areas of Tanzania

The periwinkle Littoraria scabra was collected at polluted and pristine mangrove sites along the Tanzanian coastline, including Msimbazi, Mbweni (i.e. Dar es Salaam) and Kisakasaka, Nyamanzi and Maruhubi (i.e. Zanzibar). Periwinkles were morphologically characterized, sexed and their heavy metal content was determined using ICP-MS. Analysis revealed that L. scabra from polluted areas contained higher soft tissue heavy metal levels, were significantly smaller and weighed less compared to their conspecifics from the unpolluted mangroves. The current morphological observations may be explained in terms of growth and/or mortality rate differences between the polluted and non-polluted sites. Although a variety of stressors may account for these adverse morphological patterns, our data suggest a close relationship with the soft tissue heavy metal content. Compared to soft tissue heavy metal levels that were measured in L. scabra along the same area in 1998, most metals, except for arsenic, chromium and iron have decreased dramatically.     

Phytotoxicities of fluoranthene and phenanthrene deposited on needle surfaces of the evergreen conifer, Japanese red pine (Pinus densiflora Sieb. et Zucc.)

Polycyclic aromatic hydrocarbons (PAHs) have been widely studied with respect to their carcinogenic and mutagenic effects on animals and human cells. Phenanthrene (PHE) and fluoranthene (FLU) effects on the needle photosynthetic traits of 2-year-old Japanese red pine (Pinus densiflora Sieb. et. Zucc.) seedlings were investigated. Three months after fumigation of foliage with solutions containing these PAHs (10 microM each), FLU had negative effects on net photosynthesis at near-saturating irradiance, stomatal conductance, initial chlorophyll fluorescence, and the contents of total chlorophyll, magnesium, and ribulose 1,5-bisphosphate carboxylase (rubisco) of current-year needles. PHE had similar negative effects to FLU but in lesser magnitude. The effects of the PAHs were mitigated by the addition of an OH-radical scavenger (mannitol) into the PAH solutions. PAHs deposited on the surface of pine needles may induce the generation of reactive oxygen species in the photosynthetic apparatus, a manner closely resembling the action of the herbicide paraquat.     

Sulphur transformation and deposition in the rhizosphere of Juncus effusus in a laboratory-scale constructed wetland

Sulphur cycling and its correlation to removal processes under dynamic redox conditions in the rhizosphere of helophytes in treatment wetlands are poorly understood. Therefore, long-term experiments were performed in laboratory-scale constructed wetlands treating artificial domestic wastewater in order to investigate the dynamics of sulphur compounds, the responses of plants and nitrifying microorganisms under carbon surplus conditions, and the generation of methane. For carbon surplus conditions (carbon:sulphate of 2.8:1) sulphate reduction happened but was repressed, in contrast to unplanted filters mentioned in literature. Doubling the carbon load caused stable and efficient sulphate reduction, rising of pH, increasing enrichment of S(2-) and S(0) in pore water, and finally plant death and inhibition of nitrification by sulphide toxicity. The data show a clear correlation of the occurrence of reduced S-species with decreasing C and N removal performance and plant viability in the experimental constructed wetlands.     

Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

Trace elements and stable isotopes (delta13C and delta15N) in shallow and deep-water organisms from the East China Sea

Trace elements (22) and stable isotope ratios (δ¹⁵N and δ¹³C) were analyzed in marine organisms from shallow (SW) and deep-water (DW) of the East China Sea to understand biomagnification and prey source of trace elements. In the benthic marine organisms from DW, δ¹⁵N values were negatively correlated with Ba, Cu, Ag, Mo, Sr, As, and Co concentrations. This may be due to the specific accumulation in lower trophic animals and/or the biodilution through the food web in DW. Relationships between δ¹⁵N and concentrations of Co, Cr, Bi, and Tl in fish and Ag, Bi, V, Hg, and Tl in crustaceans showed positive correlations, suggesting that trophic position was affecting the concentrations of those elements in phyla, with higher trophic animals retaining higher concentrations than the lower trophic animals. Positive correlations between δ¹³C and Rb were observed in marine organisms. Therefore, Rb may be a possible substitute of δ¹³C as tracer of prey source in the East China Sea although further investigation is required.