Nitrate-consuming processes in a petroleum-contaminated aquifer quantified using push-pull tests combined with 15N isotope and acetylene-inhibition methods

Nitrate consumption in aquifers may result from several biogenic and abiotic processes such as denitrification, assimilatory NO3- reduction, dissimilatory NO3- reduction to ammonium (DNRA), or abiotic NO3- (or NO2-) reduction. The objectives of this study were to investigate the fate of NO3- in a petroleum-contaminated aquifer, and to assess the feasibility of using single-well push-pull tests (PPTs) in combination with 15N isotope and C2H2 inhibition methods for the quantification of processes contributing to NO3- consumption. Three consecutive PPTs were performed in a monitoring well of a heating oil-contaminated aquifer in Erlen, Switzerland. For each test, we injected 500 l of test solution containing 0.5 mM Br- as conservative tracer and either 0.5 mM unlabeled NO3- or approximately 0.3 mM 15N-labeled NO3- as reactant. Test solutions were sparged during preparation and injection with either N2, Ar or 10% C2H2 in Ar. After an initial incubation period of 1.5-3.2 h, we extracted the test solution/groundwater mixtures from the same location and measured concentrations of relevant species including Br-, NO3-, NO2-, N2O, N2, and NH4+. In addition, we determined the 15N contents of N2, N2O, NH4+, and suspended biomass from 15N/14N isotope-ratio measurements. Average total test duration was 50.5 h. First-order rate coefficients (k) were computed from measured NO3- consumption, N2-15N production and N2O-15N production. From measured NO3- consumption we obtained nearly identical estimates of k for all PPTs with small 95% confidence intervals, indicating good reproducibility and accuracy for the tests. Estimates of k from N2-15N production and N2O-15N production indicated that denitrification accounted for only 46-49% of observed NO3- consumption. Production of N2-15N in the presence of C2H2 was observed during one of the tests, which may be an indicator for abiotic NO3- reduction. Moreover, 15N isotope analyses confirmed occurrence of assimilatory NO3- reduction (0.58 at.% 15N in suspended biomass) and to a smaller extent DNRA (up to 4 at.% 15N in NH4+). Our results indicated that the combination of PPTs, 15N-isotope and C2H2 inhibition methods provided improved information on denitrification as well as alternative fates of NO3- in this aquifer.     

The annual course of TCA formation in the lower troposphere: a modeling study

We present a modeling study investigating the influence of climate conditions and solar radiation intensity on gas-phase trichloroacetic acid (TCA) formation. As part of the ECCA-project (Ecotoxicological Risk in the Caspian Catchment Area), this modeling study uses climate data specific for the two individual climate regimes, namely "Kalmykia" and "Kola Peninsula". A third regime has also been included in this study, namely "Central Europe", which serves as a reference to somehow more moderate climate conditions. The simulations have been performed with a box modeling package (SBOX, photoRACM), which uses Regional Atmospheric Chemistry Mechanism (RACM) as its chemistry scheme. For this model a mechanism supplement has been developed including the reaction pathways of methyl chloroform photooxidation. The investigations are completed by a detailed sensitivity study addressing the impact of temperature and relative humidity. Atmospheric OH and HO2 concentrations and the NOx/HO2 ratio were identified as the governing quantities controlling the TCA formation trough methyl chloroform oxidation in the gas phase. Model calculations show a TCA production rate ranging between almost zero and 6.5 x 10(3) molecules cm(-3) day(-1) depending on location and season. In the Kalmykia regime the model predicts mean TCA production rates of 1.3 x 10(-4) and 5.4 x 10(-5) microg m(-3) year(-1) for the urban and rural environment, respectively. From the comparison of model calculations with measured TCA burdens in the soil ranging between 130 g m(-3) and 1750 g m(-3) we conclude that TCA formation through methyl chloroform photooxidation in the gas-phase is probably not the principal atmospheric TCA source in this region.     

Electrochemical or UV-photochemical oxidation of industrial wastes containing polar aromatic sulphonates

BACKGROUND AND INTENTION: Aromatic sulphonates other than surfactants and their hydroxy and amino-derivatives are important intermediates for the production of azo dyes. Their production on a large scale can be detrimental for the environment, if the by-products of their synthesis are not disposed of appropriately. An industrial waste, the organic components of which were mainly amino and hydroxy-substituted aromatic sulphonates, seriously endangers the environment close to an dismissed Italian industrial site. Inorganic sulphates and chlorides contained in the waste seriously hinder its disposal by incineration, since they corrode furnace walls. In this work, preliminary exploration of aqueous-phase electrochemically and photochemically induced oxidation techniques have been performed as possible alternatives to incineration. METHODS: Electrochemically-induced oxidation was experimented on individual aromatic sulphonates and on an industrial waste by electrolysing them between smooth platinum electrodes at low temperature (5 degrees C) and high current densities (0.4 A/cm2) with aqueous 0.5 M NaHSO4 electrolyte. Photochemically-induced oxidation was performed by irradiating individual aromatic sulphonates or industrial waste with a 500 W mercury lamp in the presence of sodium peroxydisulphate. RESULTS AND DISCUSSION: After 200 min electrodegradation, 90% of the original compounds disappeared, while 50% Total Organic Carbon (TOC) of an industrial waste was removed from solution after 10 hours. After 180 min UV-photodegradation, 90% of two test aromatic sulphonates disappeared, while 65% of TOC of industrial waste was removed after 5 hours. CONCLUSIONS: Two methods, electrochemical and UV-persulphate oxidation of an industrial waste, were used in order to propose a disposal procedure alternative to incineration. Electrodegradation with smooth Pt anode in 0.5 M NaHSO4 at 5 degrees C halved TOC concentration within 10 hours, while persulphate-assisted UV-photochemical oxidation with a 500 W high pressure Hg lamp abated two-thirds of TOC concentration after 5 hours. Energetic consumption of electrodegradation was 0.33 kWh/g TOC, while that of photooxidation was larger than 2 kWh/g TOC. Although both techniques can be considered efficient from a purely chemical point of view, since both are capable of wet-oxidising the aromatic sulphonates and the industrial waste, electrodegradation seems more promising than a photochemical degradation if economical considerations are also taken into account. Considering also that neither cell design nor catalyst were optimised in this preliminary study, the energy yield of electrodegradation seems likely to be largely improved.     

Biodegradation of anthracene in the roots and growth substrate of poplar cuttings

Following their exposure to anthracene, the roots of Populus nigra L. Loenen showed traces of 9 substances classed as products of biodegradation. The main substances detected were phthalic acid and 9,10-anthraquinone, followed by hydroxyanthracene and methoxyanthracene and five other compounds which could not be identified. Due to the relatively low concentration of degradation products found in the roots, further degradation to lower molecular compounds are discussed. The presence of 9,10-anthraquinone as the main product of the degradation of anthracene was also evident in the control tests with unplanted sandy substrate, although the content was higher in the planted series of tests. As a non-sterile approach was chosen, it may be assumed that a microbial degradation for 9,10-anthraquinone took place in the control series. However, it is difficult to differentiate clearly between a microbial degradation of anthracene in the substrate and metabolization in the roots due in part to the absence of specific degradation products in the various reaction areas.     

The contemporary copper cycle of Asia

A regional stock and flow model for an industrial metal was developed based on the substance-flow framework. Using this model, the contemporary copper cycle of the Asian region was constructed by aggregating country-level production and import and export data for different stages of the copper cycle. The reliability and availability of data were assessed both qualitatively and quantitatively. Asia as a region is a net importer of copper. There is a significant build-up of copper in use at a rate of nearly 3TgCu/year. The per capita generation of copper waste (0.4kgCu/(capita-year)) and the rate of secondary recovery of copper are low compared with Europe and North America. Japan's rates of use, waste generation, and recycling of copper are all much larger than the continental average. A tremendous potential exists in the region to utilize the copper content of the in-use reservoir, and subsequently to enhance copper recycling rates in the future. A set of metrics for the copper cycle is suggested in order to address sustainability issues related to resource policy and the environmental management of copper.     

Environmental Management Systems at the Industrial Park Level in China

Environmental management systems (EMSs), such as International Organization for Standardization (ISO) 14001, can be used as a tool in China by industrial park managers to improve their environmental performance. This article uses the case of the Dalian Economic and Technological Development Zone (DETDZ) to show how to establish a comprehensive environmental management system (CEMS) according to the ISO 14001 standard at the industrial park level by considering local realities. The particularly interesting feature of this case study is the use of a CEMS (in this case, ISO 14001) by the administrative group of the DETDZ to develop a more comprehensive approach to the wide range of environmental issues that they face in running the zone. In essence the goal is to address many of the issues at the level of the zone. The incentives, benefits, and barriers associated with implementing ISO 14001 are described. However, implementation of an EMS should not be thought of as the ultimate objective for an industrial parks environmental management. The next steps include encouraging further public participation and taking an integrated approach leading to an industrial ecosystem, which can realize better environmental performance at the industrial park level. Yong Geng is currently a Ph.D. candidate at Dalhousie University. Raymond Côté is a professor at Dalhousie University.     

Influence of Geoengineered Climate on the Terrestrial Biosphere

Various geoengineering schemes have been proposed to counteract anthropogenically induced climate change. In a previous study, it was suggested that a 1.8% reduction in solar radiation incident on the Earths surface could noticeably reduce regional and seasonal climate change from increased atmospheric carbon dioxide (CO₂). However, the response of the terrestrial biosphere to reduced solar radiation in a CO₂-rich climate was not investigated. In this study, we hypothesized that a reduction in incident solar radiation in a Doubled CO₂ atmosphere will diminish the net primary productivity (NPP) of terrestrial ecosystems, potentially accelerating the accumulation of CO₂ in the atmosphere. We used a dynamic global ecosystem model, the Integrated Biosphere Simulator (IBIS), to investigate this hypothesis in an unperturbed climatology. While this simplified modeling framework effectively separated the influence of CO₂ and sunlight on the terrestrial biosphere, it did not consider the complex feedbacks within the Earths climate system. Our analysis indicated that compared to a Doubled CO₂ scenario, reduction in incident solar radiation by 1.8% in a double CO₂ world will have negligible impact on the NPP of terrestrial ecosystems. There were, however, spatial variations in the response of NPP-engineered solar radiation. While productivity decreased by less than 2% in the tropical and boreal forests as hypothesized, it increased by a similar percentage in the temperate deciduous forests and grasslands. This increase in productivity was attributed to a 1% reduction in evapotranspiration in the Geoengineered scenario relative to the Doubled CO₂ scenario. Our initial hypothesis was rejected because of unanticipated effects of engineered solar radiation on the hydrologic cycle. However, any geoengineering approaches that reduce incident solar radiation need to be thoroughly analyzed in view of the implications on ecosystem productivity and the hydrologic cycle.     

A novel sex-specific and inducible monoterpene synthase activity associated with a pine bark beetle,the pine engraver,<Emphasis Type="Italic"> Ips pini</Emphasis>

Ecological interactions of conifers and coniferophagous bark beetles are determined in part by terpenoids (isoprenoids), which are major defense metabolites of conifer oleoresin. Curiously, similar compounds are important aggregation pheromones of conifer-attacking bark beetles. Terpene synthases are responsible for generating the enormous variety of terpenoid carbon skeletons found in nature. These catalysts convert short-chain prenyl diphosphates to a diverse assortment of hemiterpene, monoterpene, sesquiterpene, and diterpene natural products. While terpene synthases have frequently been characterized from plant and microbial sources, they have not yet been described in animals. Here we report the discovery of a monoterpene synthase activity in an insect, the pine engraver, Ips pini (Say) (Coleoptera: Scolytidae). Cell-free assays of I. pini revealed that geranyl diphosphate (GDP) is converted to the acyclic monoterpene myrcene in whole-body extracts from males, but not females. Furthermore, the monoterpene synthase activity in males can be induced by prior treatment with juvenile hormone III (JH III) or by feeding on phloem from the host trees, Jeffrey pine (Pinus jeffreyi Grev. &; Balf.) or red pine (Pinus resinosa Ait.). The sex-specificity and endocrine induction of this activity argue for its involvement in the biosynthesis of monoterpenoid pheromones mediated by enzymes from insect tissue. This discovery is the first example of a monoterpene synthase in the Metazoa and evokes exciting new questions about the origin, evolution, and occurrence of terpene synthases.     

Plumage coloration and nutritional condition in the great tit<Emphasis Type="Italic"> Parus major</Emphasis>: the roles of carotenoids and melanins differ

The size and coloration of some body characters seem to influence mate choice in many species. Most animal colours are either structural or based on melanin or carotenoid pigments. It has recently been suggested that carotenoid-based or structural coloration may be a condition-dependent trait, whereas melanin-based coloration is not; a difference that may be highly relevant when studying the evolution of multiple mating preferences. We tested this hypothesis in the great tit (Parus major). The size of the melanin breast band was not correlated to nutritional condition as estimated by the rate of tail growth (ptilochronology), controlling for locality, age, sex, year and season effects. However, the correlation was significant for the hue of yellow breast (carotenoid-based coloration), and the slopes of the regressions of the two pigments to growth bars differed significantly. These results suggest that the expression of the two traits may be regulated by different mechanisms.     

Inverse correlation between mitochondrial size and metabolic competence: a quantitative cytochemical study of cytochrome oxidase activity

Mitochondria are topologically closed bilayered systems where the synthesis of adenosine triphosphate (ATP) from adenosine diphosphate (ADP) and inorganic phosphate occurs via oxidative phosphorylation. The ordered architecture (and its extension) of the mitochondria (i.e. inner membrane, outer membrane and cristae) constitutes a critical topographic arrangement for their energy-providing mechanisms. Thus, quantitative estimations of the ultrastructural features of organelles preferentially stained by means of function-related cytochemical reactions reliably report on their potential to supply adequate amounts of ATP. On the basis of this rationale, we carried out a computer-assisted cytochemical study of cytochrome oxidase (COX) activity on mitochondria of different size in the cerebellar cortex of adult rats. The total intra-mitochondrial area of the cytochemical precipitates (CPA)/mitochondrion, the area (MA) and the longer diameter (F_max) of COX-positive organelles were measured. The ratio (R): CPA/MA was also calculated and referred to as the percentage of mitochondrial inner membrane area involved in COX activity. The regression analysis of R vs MA showed a significant inverse correlation (r=т.905). The fourfold increase in MA from quartiles I to IV was matched by increases in F_max and CPA, respectively, but it was also related to a 25% decrease in R. By matching quantitative cytochemical estimations of COX activity within mitochondria with the morphometric assessment of their ultrastructural features, the present study correlates size to the metabolic competence of COX-positive organelles. Quantitative cytochemistry of COX activity is currently regarded as a reliable marker of cellular metabolism; thus our findings support the hypothesis that enlargements in size are inversely correlated with the mitochondrial metabolic competence.