First evidence for a stereoselective incorporation of nonylphenol diastereomers in soil-derived organo-clay complexes

Environmental processes can affect the stereochemical properties of organic pollutants. In particular, biotic processes like microbial transformations or membrane penetration alter the ratios of enantiomers as well as diastereomers. These effects have been intensively used not only in environmental studies but also in medicine, toxicology, pharmacy, and agricultural sciences. However, in order to identify unambiguously biotic-initiated alteration of organic compounds, the knowledge on the stereoselective effect of all relevant processes is mandatory. Therefore, here we report the first evidence for a stereospecific formation of non-extractable residues of a xeniobiotic in a highly relevant soil subfraction, the organo-clay complexes. In this study, soils were spiked with labeled and unlabeled nonylphenol isomer, and incubation experiments were performed to study its long-term incorporation behavior into soil-derived organo-clay complexes under abiotic and biotic conditions. Besides the extractable particle-associated proportion especially the humic fractions comprising the bound residues have been analyzed by GC/MS. Our results from biotic experiments revealed alterations of the diastereomeric composition of the contaminant in the different soil humic subfractions. A depletion of the first eluting diastereomer as expressed by diastereomeric ratios around 0.6 has been observed for the extractable fraction, whereas the non-extractable proportion was enriched in the first diastereomer (diasteremoric ratio around 1.0). On the contrary, the diastereomeric ratios remained unaffected during the abiotic experiments (diasteremoric ratio around 0.8). These systematic observations give clear evidence that the process of microbial-assisted incorporation of nonylphenol into soil organo-clay complexes is a stereoselective process. To our knowledge, this is the first report on a stereoselective incorporation process of organic substances forming non-extractable residues. Consequently, the formation of non-extractable residues has to be considered in environmental studies dealing with stereoselective analysis of organic pollutants in soils to study their microbial transformation.     

Precipitation in Light Extinction Reconstruction

Abstract

The U.S. Environmental Protection Agency (EPA) published the Regional Haze Rule (RHR) in 1999.¹ The RHR default goal is to reduce haze linearly to natural background in 2064 from the baseline period of 2000–2004. The EPA default method^2,3 for estimating natural and baseline visibility uses the Interagency Monitoring of Protected Visual Environments (IMPROVE) formula. The IMPROVE formula predicts the light extinction coefficient from aerosol chemical concentrations measured by the IMPROVE network. The IMPROVE light scattering coefficient formula using data from 1994–2002 underestimated the measured light scattering coefficient by 700 Mm^?1, on average, on days with precipitation. Also, precipitation occurred as often on the clearest as haziest days. This led to estimating the light extinction coefficient of precipitation, averaged over all days, as the light scattering coefficient on days with precipitation (700 Mm^?1) multiplied by the percent of precipitation days in a year. This estimate added to the IMPROVE formula light extinction estimate gives a real world estimate of visibility for the 20% clearest, 20% haziest, and all days. For example, in 1993, the EPAs Report to Congress projected visibility in Class I areas would improve by 3 deciviews by 2010 across the haziest portions of the eastern United States because of the 1990 Clean Air Act Amendments. Omitted was the light extinction coefficient of precipitation. Adding in the estimated light extinction coefficient of precipitation, the estimated visibility improvement declines to <1 deci-view.     

Nitrogen cycling during seven years of atmospheric CO2 enrichment in a scrub oak woodland

Experimentally increasing atmospheric CO2 often stimulates plant growth and ecosystem carbon (C) uptake. Biogeochemical theory predicts that these initial responses will immobilize nitrogen (N) in plant biomass and soil organic matter, causing N availability to plants to decline, and reducing the long-term CO2-stimulation of C storage in N limited ecosystems. While many experiments have examined changes in N cycling in response to elevated CO2, empirical tests of this theoretical prediction are scarce. During seven years of postfire recovery in a scrub oak ecosystem, elevated CO2 initially increased plant N accumulation and plant uptake of tracer 15N, peaking after four years of CO2 enrichment. Between years four and seven, these responses to CO2 declined. Elevated CO2 also increased N and tracer 15N accumulation in the O horizon, and reduced 15N recovery in underlying mineral soil. These responses are consistent with progressive N limitation: the initial CO2 stimulation of plant growth immobilized N in plant biomass and in the O horizon, progressively reducing N availability to plants. Litterfall production (one measure of aboveground primary productivity) increased initially in response to elevated CO2, but the CO2 stimulation declined during years five through seven, concurrent with the accumulation of N in the O horizon and the apparent restriction of plant N availability. Yet, at the level of aboveground plant biomass (estimated by allometry), progressive N limitation was less apparent, initially because of increased N acquisition from soil and later because of reduced N concentration in biomass as N availability declined. Over this seven-year period, elevated CO2 caused a redistribution of N within the ecosystem, from mineral soils, to plants, to surface organic matter. In N limited ecosystems, such changes in N cycling are likely to reduce the response of plant production to elevated CO2.     

The fear of being eaten reduces energy transfer in a simple food chain

Food chain length is an important property of ecosystems, but the mechanisms maintaining it remain elusive. Classical views suggest that energetic inefficiencies (the "energy-flow hypothesis") limit food chain length, but others have argued that better explanations reside in more complex scenarios that consider the stability of food webs or the combined effects of productivity and ecosystem size. We argue that abandonment of the energy-flow hypothesis is premature. For a simple tritrophic rocky intertidal food chain, we show that the efficiency of energy transfer is strongly influenced by predation risk and consumer density. Effects tied to predation risk were particularly strong, explaining 32% of the variation in growth efficiency (compared to 15% for density effects) and reducing it by 44-76%. Hence, the stress (fear of being eaten) that predators impose on prey may be instrumental in limiting energy transfer up the food chain and thus contribute to the shortening of food chains.     

Biodegradation of hydrocarbons vapors: Comparison of laboratory studies and field investigations in the vadose zone at the emplaced fuel source experiment, Airbase Vaerløse, Denmark

The natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone can only be predicted when information about microbial biodegradation rates and kinetics are known. This study aimed at determining first-order rate coefficients for the aerobic biodegradation of 13 volatile petroleum hydrocarbons which were artificially emplaced as a liquid mixture during a field experiment in an unsaturated sandy soil. Apparent first-order biodegradation rate coefficients were estimated by comparing the spatial evolution of the resulting vapor plumes to an analytical reactive transport model. Two independent reactive numerical model approaches have been used to simulate the diffusive migration of VOC vapors and to estimate degradation rate coefficients. Supplementary laboratory column and microcosm experiments were performed with the sandy soil at room temperature under aerobic conditions. First-order kinetics adequately matched the lab column profiles for most of the compounds. Consistent compound-specific apparent first-order rate coefficients were obtained by the three models and the lab column experiment, except for benzene. Laboratory microcosm experiments lacked of sensitivity for slowly degrading compounds and underestimated degradation rates by up to a factor of 5. Addition of NH3 vapor was shown to increase the degradation rates for some VOCs in the laboratory microcosms. All field models suggested a significantly higher degradation rate for benzene than the rates measured in the lab, suggesting that the field microbial community was superior in developing benzene degrading activity.     

Anti-predatory vigilance and the limits to collective detection: visual and spatial separation between foragers

Collective detection concerns the idea that all members of a socially feeding group are alerted to an attack as long as at least one group member detects it. We found that collective detection in mixed flocks of emberizid sparrows is limited markedly by relatively small degrees of visual and spatial separation between foragers. These limits on collective detection appear to influence the degree to which flock members lower their vigilance with increasing group size (the group size effect). Specifically, the decrease in collective detection with increasing visual and spatial isolation between foragers is accompanied by a concomitant decrease in the strength of the vigilance group size effect. Explanations for the vigilance-related effects of such separation based upon a bird’s ability to monitor the vigilance behavior of flockmates can be ruled out for our experimental system. Our results also shed light on the issue of whether the vigilance group size effect is influenced more by collective detection or the simple dilution of risk with increasing group size. We argue that collective detection is not only an important determinant of the group size effect, but also that the phenomena of collective detection and risk dilution are interdependent. Received: 25 July 1995/Accepted after revision: 17 December 1995     

Some of the Nineteenth Century Origins of the Sustainability Concept

Interpreting and applying the concept of sustainable development is increasingly viewed as being the way to promulgate just and practicable economic, environmental and social policy. It is thus important that there be increased public and political awareness concerning the origins of economic theory, and its early relationship to sustainability concepts. While the term 'sustainable development' was popularised by the World Commission on Environment and Development report Our Common Future in 1987, it is generally recognised that notions of sustainability were promoted in `limits to growth' and 'green' discourses in the early 1970s (Meadows et al.: 1974, The Limits to Growth: A Report for the Club of Rome, Potomac Associates and Pan Books, London and Sydney). However, there is little acknowledgement of the way in which nineteenth century intellectuals, from a range of disciplines, conceptualised the importance of balancing economic, social and environmental sustainability in their quest for justice and the conservation of nature.There was a considerable exchange of ideas on `political economy' and nature across Europe, and later the Americas, from the middle of the eighteenth century. This discourse reached its intellectual peak in the nineteenth century. During that era there was a proliferation of literature that was aimed at improving the human condition and recognising humanity's dependence upon nature. In Europe and the USA the participants in the debate included Cantillon, Quesnay, Condorcet, Galiani, Von Hayek, Marx and George. Due to the breadth of this influential body of work, we focus here on the British Victorian thinkers such as Darwin, Malthus, Martineau and Mill. These thinkers influenced each other in developing their theories and ideas in science, politics, economics and philosophy, and were influenced in turn by an earlier generation of intellectuals, such as Adam Smith. For the Victorian thinkers, conserving nature while trying to improve the distribution of wealth was a not a paradox, but a moral duty, and for them Smith's `rational' pursuit of self-interest could only be followed if it did not interfere with 'the rules of justice'. We argue that the manner in which these thinkers conceptualised their theories and ideas represents the nineteenth century origins of sustainability concepts.     

Eclogites with a short-lived granulite facies overprint in the Moldanubian Zone, Czech Republic: petrology, geochemistry and diffusion modelling of garnet zoning

The petrology and geochemistry of a newly discovered suite of high-pressure garnet + clinopyroxene-bearing rocks from the Monotonous Series of the Moldanubian Zone of the Bohemian Massif, southwest Czech Republic have been investigated. Three types [common eclogites, quartz ± kyanite ± (clino)zoisite eclogites and garnet-hornblende-clinopyroxenites] are distinguished by petrography and geochemistry. All underwent a significant degree of partial breakdown under granulite and amphibolite facies conditions during exhumation. Important features include the growth of orthopyroxene in breakdown domains after garnet and omphacite and anorthite + spinel ± corundum ± exceedingly peraluminous sapphirine replacing kyanite. Garnet zoning and inclusion patterns support a prograde evolution from low pressures for at least some of the samples. The post-eclogite stage granulite facies overprint indicates that high temperatures prevailed during exhumation, but preservation of zoning in some garnets and the results of diffusion modelling suggest that this overprint took place over a very short time-scale. The geochemical and petrological results allow characteristic differences to be recognized between these eclogites and metabasites found in other tectonic units of South Bohemia and consequently the assigning of all high-pressure rocks to a single, now disrupted, tectonic unit is a gross simplification that seriously misrepresents the tectono-metamorphic history of the region.     

Catalytic NOx reduction with simultaneous dioxin and furan oxidation

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NOx- and CO-emissions are reduced by 90% and 20% to about 50 mg/Nm3 and below 10 mg/Nm3, respectively.