The “Tsesis” oil spill: Acute and long-term impact on the benthos

The “Tsesis” oil spill in October 1977 resulted in the release of over 1 000 tons of medium grade fuel oil in an archipelago in the brackish Baltic Sea. Considerable oil quantities reached the benthos by sedimentation. Within 16 d benthic amphipods of the genus Pontoporeia, as well as the polychaete Harmothoe sarsi Kinberg, showed reduction to less than 5% of pre-spill biomasses at the most impacted station. The clam Macoma balthica (L.) was more resistant, and showed little or no mortality, but was heavily contaminated by oil (about 2 000 μg g^-1 dry wt total hydrocarbons). The meiofauna was strongly affected, with ostracods, harpacticoids, Turbellaria and kinorhynchs showing clear reductions in abundance, while nematodes, as a group, were more resistant. In the winter following the spill gravid Pontoporeia affinis Lindström females showed a statistically significant increase in the frequency of abnormal or undifferentiated eggs. Food-chain transfer of oil to flounder [Platichthys flesus (L.)] was indicated. Not until the second summer after the spill were the first signs of recovery noted at the most heavily impacted station: Amphipods, H. sarsi and harpacticoids increased and the oil concentrations in M. balthica decreased (to about 1 000 μg g^-1). In the area where amphipods had been virtually eliminated, there was an unusually heavy recruitment of M. balthica, reaching 4 000 juveniles, of 1.5–2 mm length, per square metre, probably from settling in summer 1978. Three years after the spill Pontoporeia spp. biomass was still depressed in the most affected area, while H. sarsi showed normal biomass, and M. balthica abundance was inflated. Oil concentrations in M. balthica (about 250 μg g^-1) and flounder were only slightly elevated and the oil could no longer be confidently ascribed to “Tsesis” origin, even using GC/MS-analysis. Recovery was thus underway, but the long lifespan of M. balthica implies that the disturbed community composition may persist for many years at this station. Full recovery is likely to require more than 5 yr and may take a decade or more. An effort to evaluate the accumulated monetary loss to fishery from the accident indicates that direct costs of shoreline cleanup and vessel damage were considerably greater.     

PCB in soils and estimated soil-air exchange fluxes of selected PCB congeners in the south of Sweden

PCB concentrations were studied in different soils to determine the spatial variation over a region of approximately 11 000 km(2). PCB congener pattern was used to illustrate the spatial differences, as shown by principal component analysis (PCA). The relationship to different soil parameters was studied. PCB concentrations in soil showed a large variation between sampling-areas with median concentrations ranging between 2.3 and 332 ng g(-1) (dw). Highest concentrations were found at two sites with sandy soils, one with extremely high organic carbon content. Both sites were located on the west coast of southern Sweden. Soils with similar soil textures (i.e. sandy silt moraine) did not show any significant differences in PCB concentrations. PCB congener composition was shown to differ between sites, with congener patterns almost site-specific. PCB in air and precipitation was measured and the transfer of chemicals between the soil and air compartments was estimated. Soil-air fugacity quotient calculations showed that the PCBs in the soil consistently had a higher fugacity than the PCBs in the air, with a median quotient value of 2.7. The gaseous fluxes between soil and air were estimated using standard modelling equations and a net soil-air flux estimated by subtracting bulk deposition from gaseous soil-air fluxes. It was shown that inclusion of vertical sorbed phase transport of PCBs in the soil had a large effect on the direction of the net soil-air exchange fluxes.     

Avoiding CO2 capture effort and cost for negative CO2 emissions using industrial waste in chemical-looping combustion/gasification of biomass

Chemical-looping combustion (CLC) is a combustion process with inherent separation of carbon dioxide (CO₂), which is achieved by oxidizing the fuel with a solid oxygen carrier rather than with air. As fuel and combustion air are never mixed, no gas separation is necessary and, consequently, there is no direct cost or energy penalty for the separation of gases. The most common form of design of chemical-looping combustion systems uses circulating fluidized beds, which is an established and widely spread technology. Experiments were conducted in two different laboratory-scale CLC reactors with continuous fuel feeding and nominal fuel inputs of 300 W_th and 10 kW_th, respectively. As an oxygen carrier material, ground steel converter slag from the Linz–Donawitz process was used. This material is the second largest flow in an integrated steel mill and it is available in huge quantities, for which there is currently limited demand. Steel converter slag consists mainly of oxides of calcium (Ca), magnesium (Mg), iron (Fe), silicon (Si), and manganese (Mn). In the 300 W unit, chemical-looping combustion experiments were conducted with model fuels syngas (50 vol% hydrogen (H₂) in carbon monoxide (CO)) and methane (CH₄) at varied reactor temperature, fuel input, and oxygen-carrier circulation. Further, the ability of the oxygen-carrier material to release oxygen to the gas phase was investigated. In the 10 kW unit, the fuels used for combustion tests were steam-exploded pellets and wood char. The purpose of these experiments was to study more realistic biomass fuels and to assess the lifetime of the slag when employed as oxygen carrier. In addition, chemical-looping gasification was investigated in the 10 kW unit using both steam-exploded pellets and regular wood pellets as fuels. In the 300 W unit, up to 99.9% of syngas conversion was achieved at 280 kg/MW_th and 900 °C, while the highest conversion achieved with methane was 60% at 280 kg/MW_th and 950 °C. The material’s ability to release oxygen to the gas phase, i.e., CLOU property, was developed during the initial hours with fuel operation and the activated material released 1–2 vol% of O₂ into a flow of argon between 850 and 950 °C. The material’s initial low density decreased somewhat during CLC operation. In the 10 kW, CO₂ yields of 75–82% were achieved with all three fuels tested in CLC conditions, while carbon leakage was very low in most cases, i.e., below 1%. With wood char as fuel, at a fuel input of 1.8 kW_th, a CO₂ yield of 92% could be achieved. The carbon fraction of C₂-species was usually below 2.5% and no C₃-species were detected. During chemical-looping gasification investigation a raw gas was produced that contained mostly H₂. The oxygen carrier lifetime was estimated to be about 110–170 h. However, due to its high availability and potentially low cost, this type of slag could be suitable for large-scale operation. The study also includes a discussion on the potential advantages of this technology over other technologies available for Bio-Energy Carbon Capture and Storage, BECCS. Furthermore, the paper calls for the use of adequate policy instruments to foster the development of this kind of technologies, with great potential for cost reduction but presently without commercial application because of lack of incentives.

     

Conceptual design of an integrated heating system at LKAB Malmberget with consideration of social-environmental damage costs

LKAB Malmberget is a Swedish mining site located at Malmberget, Sweden. Seven boiler centers are located in the north part of Malmberget. There are no connections in between these boiler centers, meaning that it is a decentralized heating system. The heat generated is used to heat up buildings and for mine ventilation air mainly during the cold periods. The heat is mainly provided from electric and oil boilers. However, most boilers under use are over 20 years old, and it is time to retrofit the boiler system and infrastructure. The purpose of this work is to design and optimize the heating system by introducing an integrated concept to minimize the heat production cost.An optimization model based on the mixed integer linear programming (MILP) has been developed. Several technical options have been considered in a new centralized heating system. The optimization principle is based on two kinds of perspectives: current price and external costs. With consideration of environmental and health damage from society concerns point of view, instead of environmental taxes in the current price perspective, the monetary values of externalities due to pollutants such as CO₂, NO_x, SO₂ and particulates emitted from the heating system are included. On the basis of data input and assumptions, modeling results indicate that a lower cost could be achieved when a waste heat recovery boiler is installed at the older pelletization plant to recover sensible heat from flue gas. This technical option is the best solution or at least contributes to the best solution in all optimization results. Including the externality cost is useful for making fair evaluation of the social-environmental impacts of the alternatives.     

Re-cycling of remediated soil in Sweden: An environmental advantage?

The disposal of soil material after ex situ treatment of contaminated soil is an issue of growing concern. The handling and use of this material are surrounded by numerous regulatory, economic, technical and societal aspects that complicate or hinder re-cycling. As a consequence, the lack of means of recovery can in the long-term bias the whole remedial process. In addition, it can affect the competition between various treatment options such as ex situ, and in situ techniques and landfilling. At the same time the materials must not have any negative environmental impacts, and their usage must be compatible with existing risk assessment and management frameworks regarding contaminated land. Other concerns such as a possible distinction against “lightly” contaminated materials, waste status and public acceptance add to the complexity. This paper focuses on Swedish conditions, but does also provide an outlook concerning EU regulation. A summary of leaching and batch tests employed for re-use of soil and waste is presented as well as an overview of the eco-toxicological aspects of treated materials. The main conclusion is that re-cycling of treated soil is desirable from numerous aspects, but has to go along an adequate risk assessment.     

A case study on raw material blending for the recycling of ferrous wastes in a blast furnace

The utilisation of ferrous wastes in a blast furnace is a well established recycling process to cope with the enormous amounts of ferrous residues in the iron and steel industry. The further input flows of this process, that is especially coke and fluxes, as well as its output flows, that is pig iron and by-products, are highly dependent on the blending of the ferrous wastes while they differ highly in the revenues gained for the treatment and their chemical composition. So far, no planning approach exists for the blending of the residues on the operational planning level that models the dependency of the costs and revenues on the raw material blend and the thermodynamic reactions in the recycling processes adequately. Therefore we present an approach for this operational production planning problem focusing on an integration of such a sufficiently detailed modelling of the underlying metallurgical processes into the planning model. The basis of our approach is a thermodynamic simulation of the processes. From this simulation we derive linear input-output functions for the relevant material and energy flows by using multiple linear regression. These input–output functions form the core of our blending model developed for the planning task. The model is implemented as an integrated decision support system. Exemplary application results are given. These results validate the approach and show that ecological the economic optimisation leads also to results which are advantageous in terms of resource efficiency and emission reduction. Though developed for a specific recycling process, the methodology can be transferred to other metallurgical (recycling) processes, as well as other parts of the process industries, and is therefore of high relevance.     

History of Fly Ash Collection at the South Charleston Plant Union Carbide Corporation—Chemicals Division

This report summarizes the installation and operation of fly ash collection and disposal equipment at the South Charleston Plant and includes installation costs, replacement costs based on present-day cost factors, as well as performance data, and maintenance and operating costs.     

Teratogenicity of bifenox and nitrofen in rodents

Abstract

The teratogenicity of the diphenyl ether herbicide bifenox [2,4‐dichlorophenyl 3'‐carboxymethyl‐4'‐nitrophenyl ether] was compared to that of nitrofen [2,4‐dichlorophenyl 4'‐nitrophenyl ether] in rats and in mice. Neither compound increased prenatal mortality in mice. Because nitrofen causes both malformations that are compatible with survival to weaning and a high incidence of perinatal (but not of fetal) mortality, emphasis was placed on postnatal parameters of bifenox toxicity. In rats, bifenox caused a low incidence of “bloody tears”;, but it did not decrease survival to term or to weaning in rats or mice, and did not reduce Harderian gland weight in mice. Because the weight of the Harderian glands is a more objective measure of their status than is the presence of an eye discharge, it is concluded that bifenox is not teratogenic at the levels administered. Nitrofen decreased litter size, pup weight, and Harderian gland weight in mice.     

Characterization and classification of complex PAH samples using GC-qMS and GC-TOFMS

The aim of this study was to compare the polycyclic aromatic hydrocarbon (PAH) contents in a number of complex samples, including soil samples from industrial sites, anti-skid sand, urban dust and ash samples from municipal solid waste incinerators. The samples were characterized by routine analysis of PAHs (gas chromatography–quadrupole mass spectrometry) and gas chromatography–time of flight mass spectrometry (GC–TOFMS). Classification of the samples by principal component analysis (PCA) according to their composition of PAHs revealed that samples associated with traffic and the municipal incinerator formed homogeneous clusters, while the PAH-contaminated soils clustered in separate groups. Using spectral data to resolve co-eluting chromatographic peaks, 962 peaks could be identified in the GC–TOFMS analysis of a pooled sample and 123–527 peaks in the individual samples. Many of the studied extracts included a unique set of chemicals, indicating that they had a much more diverse contamination profile than their PAH contents suggested. Compared to routine analysis, GC–TOFMS provided more detailed information about each sample and in this study a large number of alkylated PAHs were found to be associated with the corresponding unsubstituted PAHs. The possibility to filter peaks according to different criteria (e.g. to include only peaks that were detected in the analysis of another sample) was explored and used to identify unique as well as common compounds within samples. This procedure could prove to be valuable for obtaining relevant chemical data for use in conjunction with results from various biological test systems.     

Ah Receptor Agonists in UV-exposed Toluene Solutions of Decabromodiphenyl Ether (decaBDE) and in Soils Contaminated with Polybrominated Diphenyl Ethers (PBDEs) (9 pp)

Goal, Scope and Background The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study, mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE. In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs. Soils were also exposed to UV-light to study changes in AhR agonist levels. Methods Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB (280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive, chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure, were analysed with the DR-Calux. Results and Discussion Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis. The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible for this. Recommendations and Perspective . The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed from decaBDE even though the exact identities of these compounds were not known. Conclusion Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays allows a rapid evaluation of toxicological relevance.