Testing of hydrotalcite-based sorbents for CO2 and H2S capture for use in sorption enhanced water gas shift

The feasibility of the sorption enhanced water gas shift (SEWGS) process under sour conditions is shown. The sour-SEWGS process constitutes a second generation pre-combustion carbon capture technology for the application in an IGCC. As a first critical step, the suitability of a K₂CO₃ promoted hydrotalcite-based CO₂ sorbent is demonstrated by means of adsorption and regeneration experiments in the presence of 2000 ppm H₂S. In multiple cycle experiments at 400 °C and 5 bar, the sorbent displays reversible co-adsorption of CO₂ and H₂S. The CO₂ sorption capacity is not significantly affected compared to sulphur-free conditions. A mechanistic model assuming two different sites for H₂S interaction explains qualitatively the interactions of CO₂ and H₂S with the sorbent. On the type A sites, CO₂ and H₂S display competitive sorption where CO₂ is favoured. The type B sites only allow H₂S uptake and may involve the formation of metal sulphides. This material behaviour means that the sour-SEWGS process likely eliminates CO₂ and H₂S simultaneously from the syngas and that an almost CO₂ and H₂S-free H₂ stream and a CO₂ + H₂S stream can be produced.     

Practical Applications of Stacks to Minimize Pollution Problems

“Rules of thumb” for stack design have been developed for use on problems where extensive studies cannot be justified or where quantitative design data are unavailable. The application of these rules to a practical stack design problem is discussed. The IBM 704 computer has been used for rapid yet rigorous stack design studies. The computer procedures for design are discussed and its application to a practical problem is described in detail.     

Bioassay responses and effects on benthos after pilot remediations in the delta of the rivers Rhine and Meuse

Chemical and biological monitoring was carried out for 5 years following pilot remediations at two locations in the Rhine-Meuse delta. The remediations consisted of partial excavation of the contaminated sediments, followed by applying a clean layer of sandy material on top. After the remediation, a new silty sediment top layer was formed exhibiting a lower toxicity in five sediment/sediment pore water bioassays. Compared to the unremediated sites, lower metal and PAH concentrations were found at the remediated sites, but in one location at the same time elevated HCH, PCB and HCB levels were recorded. One year after the remediation, the differences became smaller, although effects-based classification showed that the remediated site showed a higher quality up to the last year. In both remediated sites a rapid recolonization of nematodes, oligochaetes and chironomids was observed, while the recolonization by bivalves was slower. A few years after the remediation the differences decrease.     

Estrogenic and esterase-inhibiting potency in rainwater in relation to pesticide concentrations,sampling season and location

In a year-round monitoring program (1998), pesticide composition and toxic potency of the mix of pollutants present in rainwater were measured. The goal of the study was to relate atmospheric deposition of toxic potency and pesticide composition to each other and to sampling period and local agricultural activity. Rainwater was collected in 26 consecutive periods of 14 days in a background location (BACK) and in two locations representative for different agricultural practices, i.e. intensive greenhouse horticulture (HORT) and flower bulb culture (BULB). Samples were chemically analyzed for carbamate (CARB), organophosphate (OP) and organochlorine (OC) pesticides and metabolites. Esterase inhibiting potency of rainwater extracts was measured in a specially developed bio-assay with honeybee esterases and was expressed as an equivalent concentration of the model inhibitor dichlorvos. Estrogenic potency of the extracts was measured in the ER-CALUX reporter gene assay and was expressed as an equivalent concentration of estradiol. Multivariate principal component analysis (PCA) techniques proved to be valuable tools to analyze the numerous pesticide concentrations in relation to toxic potency, sampling location, and sampling season. Pesticide composition in rainwater depended much more on sampling season than on sampling location, but differences between and were mainly attributed to local differences in agricultural practice. On average, the esterase inhibiting potency exceeded the maximum permissible concentration set for dichlorvos in The Netherlands, and was significantly higher in than in and . Esterase inhibition correlated significantly with OP and CARB concentrations, as expected given the working mechanism of these insecticides. The estrogenic potency incidentally exceeded NOEC levels reported for aquatic organisms and was highest in . Although estrogenic potency of rainwater correlated with OC concentrations, the ER-CALUX responses could not be attributed to any particular pesticides. Besides, the contribution of non-analyzed xeno-estrogens as alkylphenol(-ethoxylates) and bisphenol-A to the estrogenic potency of rainwater could not be excluded. Further research should focus on the chemical identification of estrogenic compounds in rainwater. In addition, more attention should be given to the ecological consequences of atmospheric deposition of individual pesticides and of total toxic potencies that regularly exceed environmental criteria for Dutch surface waters and/or toxic threshold values for aquatic organisms.     

Analysis of acidic pesticides using in situ derivatization with alkylchloroformate and solid-phase microextraction (SPME) for GC-MS.

A solid-phase microextraction (SPME) method was developed for the analysis of acidic pesticide residues in water. The method utilizes in situ derivatization with butylchloroformate (BuCF), followed by on-line SPME extraction using a PDMS fibre, and analysis by GC-MS. Derivatives of the phenoxy acids mechlorprop (MCPP), dichlorprop (DCPP), MCPA and 2,4-D and their phenol degradation products 4-chloro-2-methylphenol and 2,4-dichlorophenol (DCP) were identified. Detection limits at 0.16-2.3 microg/l were achieved. Optimization of derivatization, ion strength, extraction time, SPME-fibre, desorption time and temperature are described. Standard curves in the range 0.5-10.0 microg/l were fitted to a second-degree polynomial. Standard deviation (n = 5) was below 10% for the phenol derivatives, but 20-50% for the phenoxy acids. For method verification groundwater samples from a field experiment were screened for content of MCPP and compared to the results from the HPLC analysis. A good agreement was obtained with respect to identification of positive samples, even though concentrations measured by the SPME were lower than with HPLC. Even if the precision and accuracy do not meet the demands for a strictly quantitative analysis, the SPME method is suitable for screening, because it is cheap, it can be automated, and uses smaller amounts of potential harmful solvents. Also, the method is less labour-intensive, as it requires a minimum of sample preparation when compared to traditional analyses. The acidic pesticides bentazon, dicamba, bromoxynil, ioxynil, dinoseb and DNOC were included in the study but could not be analysed by the current method.     

Screening of thyroid gland histology in organohalogen-contaminated glaucous gulls (Larus hyperboreus) from the Norwegian Arctic

The associations between blood organohalogen contaminant (OHC) concentrations and thyroid gland histology were studied in 10 adult female glaucous gulls (Larus hyperboreus) from the Norwegian Arctic (Bjørnøya) during the incubation period. This histological investigation was undertaken as previous glaucous gull studies from the same area reported negative relationships between circulating OHC concentrations and thyroid hormone levels. Organohalogen concentrations have previously been associated with altered blood plasma thyroid hormone concentrations, as a result of parenchymal thyroid gland alterations and perturbation of the hypothalamic-pituitary-thyroid (HPT)-axis. In this study, PCB (range: 186–1027 ng g^?1ww), DDT (77–203 ng g^?1ww) and chlordane (18–65 ng g^?1ww) concentrations dominated the blood plasma OHC profile in incubating female glaucous gulls. High density of small follicles accompanied by follicular epithelial cell proliferations was seen in thyroid glands in seven of 10 gulls. Focal thyroiditis and nodular hyperplasia were found in two birds. No significant differences in plasma OHC concentrations were noted between gulls exhibiting high density of small follicles and cell proliferations and those birds not showing histological changes. Based on these findings, data suggest that the histological changes in thyroid glands of OHC-contaminated female glaucous gulls may be due to natural variance, although an OHC-induced thyroid stimulating hormone (TSH) perturbation resulting in epithelial cell hyperplasia and increased follicular density cannot be ruled out and remains to be verified. Hence, a large-scale histological study is required, in order to elaborate the potential linkage between changes in thyroid gland histology, OHC exposure and regulation of the HPT-axis in the Arctic-breeding glaucous gull.     

Melanin-based colour polymorphism signals aggressive personality in nest and territory defence in the tawny owl (Strix aluco)

Nest and territory defence are risky and potentially dangerous behaviours. If the resolution of life history trade-offs differs between individuals, the level of defence may also vary among individuals. Because melanin-based colour traits can be associated with life history strategies, differently coloured individuals may display different nest and territory defence strategies. We investigated this issue in the colour polymorphic tawny owl (Strix aluco) for which plumage varies from dark to light reddish melanic. Accordingly, we found that (1) our presence induced a greater response (flying around) from dark-coloured than light-coloured females and (2) dark reddish males suffered lower nest predation rates than light-coloured males. In experimentally enlarged broods, the probability that females reacted after we played back the hoot calls of a stranger male was higher if these females were lighter reddish; the opposite pattern was found in experimentally reduced broods with dark parents being more reactive than light parents. Finally, darker females alarmed more frequently when paired with a light than with a dark male, suggesting that partners adjust their behaviour to each other. We also tested whether colouration is used as a signal by conspecifics to adjust the level of their defensive behaviour. Accordingly, breeding females responded more vigorously to a dark than a light reddish stuffed tawny owl placed beside their nest. We conclude that melanin-based colouration is a signal of alternative nest and territory defence behaviour that depends on ecological factors.     

Uptake of injected PCBs from the yolk by the developing chicken embryo

In this study, PCB uptake by the developing chicken embryo was measured after injection of two different doses of Aroclor 1254 before incubation. It was shown that 2% of the injected PCBs was absorbed on day 13, and this increased exponentially to 18% at day 19. This exponential increase could be described by a similar model for both low and high injection doses. Differences in injection dose resulted in corresponding differences in concentration in the embryos. Lipid corrected concentrations in the embryo were stable through development from day 13 up to day 19 and could be predicted from injection doses by using a conversion factor of 0.15 g(-1).     

Ecotoxicological suitability of floodplain habitats in The Netherlands for the little owl (Athene noctua vidalli)

This study describes the actual risks of exposure to contaminants, which little owls (Athene noctua vidalli) face in Dutch river floodplains. The results indicate that PCBs pose a risk: not only are levels in little owls from floodplains higher than levels found in little owls from a reference site but the PCB patterns in owls from the floodplains also indicate induction of hepatic cytochrome P450 enzymes by dioxin like compounds, possibly PCBs. Of the heavy metals, only cadmium is thought to pose a risk in certain conditions, for example, when little owls are feeding only on earthworms over a prolonged period of time. The results do not indicate any effects on the occurrence of prey items of the little owl like for instance earthworm, beetles and shrews. Hence, it is not expected that little owls will be affected by diminishing prey availability due to contamination.