Dioxins,chlorophenols and other chlorinated organic pollutants in colloidal and water fractions of groundwater from a contaminated sawmill site

BACKGROUND, AIM, AND SCOPE: The distribution of chlorinated organic contaminants in groundwater and the importance of colloids were studied in groundwater from a sawmill site contaminated by chlorophenol preservatives. MATERIALS AND METHODS: The groundwater was fractionated into three different size ranges: (1) >0.7 mum, (2) 0.4-0.7 mum and (3) 0.2-0.4 mum and the filtered water phase. The concentrations of chlorophenols (CP), chlorinated phenoxy phenols (PCPP), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD) were determined in each fraction. The colloids were characterised regarding the chemical composition using X-ray photoelectron spectroscopy (XPS). RESULTS: Chlorophenols were mostly found in the water fraction and PCDD/Fs were found almost exclusively in the particulate fractions. For example, the filtered water phase contained 2,100 mug l(-1) and 0.72 ng l(-1) for CPs and PCDD/Fs, respectively, and the particulate fractions contained 27 mug l(-1) and 32 ng l(-1) for CPs and PCDD/Fs, respectively. XPS evaluation of the particulate phases showed no correlation between the surface chemistry of the particle properties and the distribution of chlorinated compounds. DISCUSSION: The results suggest that groundwater transport of CPs, PCPPs, PCDEs and PCDD/Fs may occur from contaminated sawmill sites and that the colloid-facilitated transport, especially of PCDD/Fs, is substantial. The results correlated well with previous studies of compounds sorbed to dissolved organic carbon, which indicate that dissolved and colloidal organic carbon facilitated the transport of PCDEs, PCDFs and PCDDs particularly. CONCLUSIONS: Several classes of chlorinated compounds were readily detected in the groundwater samples. Due to the differences in their physicochemical properties, CPs, PCPPs, PCDEs and PCDD/Fs vary in their partitioning between colloidal fractions and the filtered groundwater. The proportion of the bound fraction increased with an increasing hydrophobicity of the chlorinated compounds. The groundwater transport of colloid-associated pollutants from the site may be significant. RECOMMENDATIONS AND PERSPECTIVES: The results imply that colloidal particles <0.7 mum are freely mobile in groundwater from this site. The groundwater transport of colloid-associated pollutants may be significant. However, the extent of the problem is not yet known and, thus, further research is needed to evaluate the impact of colloidal transport of hydrophobic organic contaminants. In Sweden alone, 400 to 500 sawmill sites are estimated to be contaminated with PCDD/Fs as a result of the former use of CP-based wood preservatives. The widespread use of CP mixtures for a variety of applications, including wood preservation, indicates that potential colloidal transport will be an issue of concern in many countries.     

Biological effect monitoring in dab (<Emphasis Type="Italic">Limanda limanda</Emphasis>) using gene transcript of CYP1A1 or EROD—a comparison

BACKGROUND, AIM, AND SCOPE: Gene expression analyses with real-time (RT)-polymerase chain reaction (PCR) gains importance in marine monitoring. This new technique has to be compared to the classical approaches like the well known biomarker ethoxyresorufin-O-deethylase (EROD) to test their suitability for monitoring programmes. The goal of the present study is to compare EROD activity and CYP1A1 mRNA expression in the important monitoring fish species dab (Limanda limanda) and to answer the question of whether these parameters reflect the polycyclic aromatic hydrocarbon (PAH) contamination of the fish. Further on, glyceraldehyd-3-phosphate dehydrogenase (GAPDH) was investigated as a potential housekeeping gene. MATERIALS AND METHODS: Female dab were caught in the summer of 2004 in the North Sea and in the Baltic. EROD activity was determined in liver samples by a kinetic fluorimetric assay according to a standard protocol. The gene expression of CYP1A (cytochrome P450 1A) and GAPDH were determined by means of RT-PCR. Results were compared to gonado somatic index and to the concentration of PAH metabolite 1OHPyr (1-hydroxypyrene) analysed in the bile fluids of the fish, respectively. RESULTS: Dab from all stations showed a considerable individual variation in the levels of both CYP1A mRNA and EROD. Highest mean values for CYP1A mRNA and EROD were detected in the northern part of the sampling area. In contrast, the PAH metabolite 1OHPyr was found at the highest concentration in fish caught near the German coast. CYP1A mRNA and EROD showed only a minor but significant correlation (r = 0.32, p < 0.05, n = 123). 1OHPyr in bile correlated significantly (p < 0.05) with the amount of GAPDH mRNA content in the liver. DISCUSSION: The significant but low correlation of CYP1A mRNA and EROD activity on an individual basis illustrates that these two parameters are apparently not closely linked. However, maximum EROD values correspond with maximum CYP1A mRNA concentrations when station means are regarded. Because EROD and CYP1A mRNA in dab follow different physiological principles, their application will lead to related but not identical monitoring results. This should be taken into account when future marine monitoring programmes are designed. The results also indicate that PAH are not the crucial factor for CYP1A and EROD levels in dab from the off-shore areas in the North Sea. This is remarkable because the PAH metabolism is known to be CYP1A-dependent and the widely used biomarker EROD has been recommended for monitoring PAH-related effects in fish from the North Sea. Due to a correlation between GAPDH and 1OHPyr, GAPDH was not suitable as housekeeping gene for dab. CONCLUSIONS: Neither the results from EROD nor from CYP1A1 mRNA measurements in dab reflected their exposure to PAH as measured by the PAH metabolite 1OHPyr. Thus, the question arises of whether EROD or CYP1A mRNA is a suitable biomarker at all to indicate PAH exposure in dab from the open North Sea. RECOMMENDATIONS AND PERSPECTIVES: For future biological effect monitoring, it is advisable to measure more and predominately independent parameters by RT-PCR and to incorporate more components of the detoxification system.     

Conversion of Concentrated Solar Thermal Energy into Chemical Energy

When a concentrated solar beam is irradiated to the ceramics such as Ni-ferrite, the high-energy flux in the range of 1500–2500 kW/m² is absorbed by an excess Frenkel defect formation. This non-equilibrium state defect is generated not by heating at a low heating-rate (30 K/min), but by irradiating high flux energy of concentrated solar beam rapidly at a high heating rate (200 K/min). The defect can be spontaneously converted to chemical energy of a cation-excess spinel structure (reduced-oxide form) at the temperature around 1773 K. Thus, the O₂ releasing reaction (α-O₂ releasing reaction) proceeds in two-steps; (1) high flux energy of concentrated solar beam absorption by formation of the non-equilibrium Frenkel defect and (2) the O₂ gas formation from the O^2? in the Frenkel defect even in air atmosphere. The 2nd step proceeds without the solar radiation. We may say that the 1st step is light reaction, and 2nd step, dark reaction, just like in photosynthesis process.     

Spectroscopic Analysis of NIR-Dye Sensitization in Bulk Heterojunction Polymer Solar Cells

The photovoltaic conversion efficiency for near-infrared (NIR) sunlight is improved successfully by dye sensitization of bulk heterojunction polymer solar cells, in which the active layer was prepared by a ternary blend of poly(3-hexylthiophene), a fullerene derivative (1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]-methanofullerene), and an NIR dye, silicon phthalocyanine bis(trihexylsilyl oxide). The mechanism of the NIR-dye sensitization is studied by femtosecond transient absorption spectroscopy.     

Monitoring the Multi-Year Carbon Balance of a Subarctic Palsa Mire with Micrometeorological Techniques

This article reports a dataset on 8 years of monitoring carbon fluxes in a subarctic palsa mire based on micrometeorological eddy covariance measurements. The mire is a complex with wet minerotrophic areas and elevated dry palsa as well as intermediate sub-ecosystems. The measurements document primarily the emission originating from the wet parts of the mire dominated by a rather homogenous cover of Eriophorum angustifolium. The CO₂/CH₄ flux measurements performed during the years 2001–2008 showed that the areas represented in the measurements were a relatively stable sink of carbon with an average annual rate of uptake amounting to on average ?46 g C m^?2 y^?1 including an equally stable loss through CH₄ emissions (18–22 g CH₄–C m^?2 y^?1). This consistent carbon sink combined with substantial CH₄ emissions is most likely what is to be expected as the permafrost under palsa mires degrades in response to climate warming.     

Terrain Discontinuity Effects in the Regional Flow of a Complex Karstified Aquifer

Karst aquifers are characterized by spatial heterogeneity due to the presence of highly permeable channels and conduits in low-permeable fractured rocks (matrix block). Recent studies have reported a close relationship between surface and subsurface water in karstic regions due to the water flow through a complicated network of paths formed by fracture intersections. Subsurface flow in karstified aquifers ranges between conduit flow, in large passages with relatively high flow velocities, and diffuse flow, in the matrix block where Darcy’s law is still valid. In this paper, we present the simulation of a complex karstified aquifer system in Crete, Greece, where the presence of main faults drastically affects the regional flow. A discrete fracture approach in conjunction with an equivalent porous medium approach was adopted to simulate the mixed flow in the area of interest. The simulation results have shown that the length and the orientation of the dominant faults, primarily during the rainy season, affect the flow field.     

How Do River Nitrate Concentrations Respond to Changes in Land-use? A Modelling Case Study of Headwaters in the River Derwent Catchment,North Yorkshire,UK

A combined semi-distributed hydrological model (CASCADE/QUESTOR) is used to evaluate the steady-state that may be achieved after changes in land-use or management and to explore what additional factors need to be considered in representing catchment processes. Two rural headwater catchments of the River Derwent (North Yorkshire, UK) were studied where significant change in land-use occurred in the 1990s and the early 2000s. Much larger increases in mean nitrate concentration (55%) were observed in the catchment with significant groundwater influence (Pickering Beck) compared with the surface water-dominated catchment (13% increase). The increases in Pickering Beck were considerably greater than could be explained by the model in terms of land-use change. Consequently, the study serves to focus attention on the long-term increases in nitrate concentration reported in major UK aquifers and the ongoing and chronic impact this trend is likely to be having on surface water concentrations. For river environments, where groundwater is a source, such trends will mask the impact of measures proposed to reduce the risk of nitrate leaching from agricultural land. Model estimates of within-channel losses account for 15–40% of nitrate entering rivers.     

A Spatially Explicit Model for Estimating Annual Average Loads of Nonpoint Source Nutrient at the Watershed Scale

The overloaded nonpoint source (NPS) nutrients in upper streams always result in the nutrient enrichment at lakes and estuaries downstream. As NPS pollution has become a serious environmental concern in watershed management, the information about nutrient output distribution across a watershed has been critical in the designing of regional development policies. But existing watershed evaluation models often encounter difficulties in application because of their complicated structures and strict requirements for the input data. In this paper, a spatially explicit and process-based model, Integrated Grid’s Exporting and Delivery model, was introduced to estimate annual in-stream nutrient levels. Each grid cell in this model was regarded as having potentials of both exporting new nutrients and trapping nutrients passing by. The combined nutrient dynamics of a grid is mainly determined by the grid’s features in land use/land cover, soil drainage, and geomorphology. This simple-concept model was tested at some basins in north Georgia in the USA. Stations in one basin were used to calibrate the model. Then an external validation was employed by applying the calibrated model to stations in the other neighbor basins. Model evaluation statistics implied the model’s validity and good performance in estimating the annual NPS nutrients’ fluxes at the watershed scale. This study also provides a promising prospect that in-stream annual nutrient loads can be accurately estimated from a few public available datasets.     

Dynamic Games in the Economics and Management of Pollution

The paper provides a survey of the literature which utilizes dynamic state-space games to formulate and analyze intertemporal, many decision-maker problems in the economics and management of pollution.     

Development of Dissolved Oxygen Model for a Highly Variable Flow River: A Case Study of Ravi River in Pakistan

A framework for dissolved oxygen (DO) modeling of the Ravi River has been developed based on a combination of laboratory measurements and field and monitoring data. Both the classical Streeter-Phelps (CSP) and the modified Streeter-Phelps (MSP) models are used for DO simulations. The MSP model considers the carbonaceous biochemical oxygen demand (CBOD) and nitrogenous biochemical oxygen demand (NBOD) separately, whereas the CSP model is evaluated considering only the CBOD and NBOD is incorporated in the overall BOD utilization rate. CBOD, NBOD and BOD rates have been determined through long-term BOD analysis of five main wastewater outfalls and two surface drains discharging into the Ravi River over a 98 km stretch. Analysis by Thomas Method manifests strong coefficient of determination “R²” between 0.72 and 0.98 for all the three types of BOD rates. Sensitivity analyses have also been carried out to find out a suitable reaeration rate formula for highly variable flows in the Ravi River. The CSP model results based on classical approach of considering only CBOD show significant difference between the model predictions and field measurements suggesting that NBOD needs to be incorporated for the model development. The dissolved oxygen values calculated using the MSP model and the CSP model based on overall BOD rate are in close agreement with field measurements and are thus suitable to model DO levels in the Ravi River.