Simulation des Nitratabbaus im Grundwasser

Ten reaction vessels containing 1 m³ were used as the experimental arrangement. They were filled with coarse sand or fine gravel and installed 60 cm below the floor. The pore volume (water saturation) was 227… 260 l. Anaerobic conditions were established by the addition of 6 g glucose at storage. The reactors were given tap water with 50 and 200 mg/l NO from KNO₃ in such a way that a volumetric rate of flow of 0.2, 0.4 and 0.8 l/d was created. The volumetric rates of flow corresponded to the natural recharge of groundwater, the recharge of groundwater under the conditions of irrigation and the conditions of an intensive wastewater ground treatment. In the effluent from the reaction vessels the nitrate concentration was determined every month. It was stationary from the 7th to the 55th month after the beginning of the experiment. The experiments are evaluated by means of a model which takes into account the diffusion, convection and kinetics of the nitrate degradation according to Michaelis-Menten. A simple method for solving homogeneous non-linear differential equations of the second order is proposed. The experimental and model results show a good agreement and prove the very slow nitrate degradation in the groundwater with k_M = 210 mg/l, v_max = 1.5 mg/l · d or k₁ = 0.005 d^?1.     

Einsatz einer konstruierten Mischkultur zur Verwertung von Mischsubstraten mit inhibierend wirkenden Substanzen

By way of introduction the general fundamentals and kinetic setups of the competitive and non-competitive as well as substrate inhibition of cultures of microorganisms are stated. Investigated on a laboratory scale is the degradation of liquid pig slurry in a 600-1 stirring fermenter with discontinuous addition (pO₂≧=30 = saturation) of methanol as external substrate by a yeast mixed culture of Metschnikowia and Pichia membranifaceans to utilize the steam-volatile fatty acids (12 g/l) and of Acetobacter methanolicus to utilize methanol. A stable fermentation with stable residual concentrations of 235 mg/l fatty acids, 142 mg/l mH₄-N an 100 … 300 mg/l methanol for aperiod of 2400 h can be achieved.     

Biologischer Abbau von 2,4-Dinitrotoluol in einer kontinuierlich betriebenen Versuchsanlage und kinetische Untersuchungen

Biological Degradation of 2,4-Dinitrotoluene in a Continuous Bioreactor and Kinetic Studies Experimental results on the aerobic biological degradation with complete mineralization of 2,4-dinitrotoluene (2,4-DNT) are presented. A culture of Pseudomonas sp. DNT from Spain and Nishino was used. The degradation was examined with batch cultures for the determination of kinetic and stoichiometric coefficients. Further experiments were carried out with a continuous culture in a fixed-bed reactor with recirculation in order to obtain high degradation rates. The reactor was packed with ceramic Raschig rings (55 mL) and had a liquid reaction volume of 160 mL. The minimal salt media from Spanggord et al. with and without (NH₄)₂S)₄ as nitrogen source was used as substrate. 2,4-DNT was the sole source of carbon and energy. From batch experiments a yield coefficient Y_B/S = (0.30 ± 0.05) g g^?1 was calculated from a mass balance of the elements. This result was confirmed by calculations using literature data. Fitting the experimental data to the Monod equation, μ_max = 0.1 h^?1 and K_S = 0.01…0.03 mmol L^?1 were obtained. It was demonstrated by batch experiments that 2,4-DNT is not only used as the source of carbon and energy but also as the nitrogen source. In the fixed-bed reactor, a degradation of 92…97% was reached with a maximal 2,4-DNT load of 95 mg L^?1 h^?1. The rate of continuous degradation could be described by a pseudo-first-order reaction (k = 9.73 h^?1). The complete mineralization of 2,4-DNT was verified by the measurement of DOC and the formed nitrite and nitrate. The formed nitrite was nitrified simultaneously. It was demonstrated by these experiments that large scale biological treatment of industrial effluent containing 2,4-DNT may be successful.     

Estimation of southern resident killer whale exposure to exhaust emissions from whale-watching vessels and potential adverse health effects and toxicity thresholds

Southern resident killer whales in British Columbia and Washington are exposed to heavy vessel traffic. This study investigates their exposure to exhaust gases from whale-watching vessels by using a simple dispersion model incorporating data on whale and vessel behavior, atmospheric conditions, and output of airborne pollutants from the whale-watching fleet based on emissions data from regulatory agencies.Our findings suggest that current whale-watching guidelines are usually effective in limiting pollutant exposure to levels at or just below those at which measurable adverse health effects would be expected in killer whales. However, safe pollutant levels are exceeded under worst-case conditions and certain average-case conditions. To reduce killer whale exposure to exhaust we recommend: vessels position on the downwind side of whales, a maximum of 20 whale-watching vessels should be within 800 m at any given time, viewing periods should be limited, and current whale-watch guidelines and laws should be enforced.     

Copper and sewage inputs from recreational vessels at popular anchor sites in a semi-enclosed Bay (Qld, Australia): estimates of potential annual loads

Environmental impacts of vessels are well documented; Cu pollution as result of Cu based antifouling paints and nutrient pollution (such as N) from marine sewage are two examples of such disturbances. Understanding environmental impacts as well as the use of coastal waterways by recreational vessels is of concern to regulatory authorities, waterway users and local residents. In this study more than 55 aerial surveys were conducted of selected popular anchorages in eastern Moreton Bay, Queensland, Australia. Numbers of recreational vessels at certain times during the year were used in multiple linear regression analyses to develop predictive models for recreational vessel numbers. Over one year approximately 10,000 locally registered recreational craft (>6m length overall) generated an estimated 59,000 vessel nights. With Cu leaching rates from the literature, and estimates of sewage inputs (assuming little or no use of pump-out facilities), load estimates associated with overnight use of 20 popular anchor sites were calculated as 141+/-46 kg of Cu and 1.17+/-0.38 t of nitrogen (N) annually. More importantly, the models showed vessel activity to be highly variable, and focused at peak holiday times, with 14% of vessel activity and associated pollutant loads entering the environment during Christmas and Easter. This study highlighted the inherent difficulties in managing a popular maritime amenity and Marine Parks such as the Moreton Bay Marine Protected Area, Queensland, Australia with its variety of stakeholders and types and intensities of uses.     

Comparison of continuum and pore-scale models of nutrient biodegradation under transverse mixing conditions

Recent studies indicate that during in situ bioremediation of contaminated groundwater, degradation occurs primarily along transverse mixing zones. Classical reactive-transport models overpredict the amount of degradation because solute spreading and mixing are not distinguished. Efforts to correct this have focused on modifying both dispersion and reaction terms, but no consensus on the best approach has emerged. In this work, a pore-scale model was used to simulate degradation along a transverse mixing zone between two required nutrients, and a continuum model with fitted parameters was used to match degradation rates from the pore-scale model. The pore-scale model solves for the flow field, concentration field, and biomass development within pore spaces of porous medium. For the continuum model, the flow field and biomass distributions are assumed to be homogeneous, and the fitting parameters are the transverse dispersion coefficient (D_T) and maximum substrate utilization rate (k_S,c). Results from the pore-scale model show that degradation rates near the system inlet are limited by the reaction rate, while degradation rates downgradient are limited by transverse mixing. For the continuum model, the value of D_T may be adjusted so that the degradation rate with distance matches that from the pore-scale model in the mixing-limited region. However, adjusting the value of k_S only improves the fit to pore-scale results within the reaction-limited region. Comparison with field and laboratory experiments suggests that the length of the reaction rate-limited region is small compared to the length scale over which degradation occurs. This indicates that along transverse mixing zones in the field, values of k_S are unimportant and only the value of D_T must be accurately fit.     

Oxidative Degradation of Orange II Dye in Water with Raw and Acid‐Treated ZnO,and MnO2

Commercial ZnO, MnO₂, and their acid‐treated forms were used as catalysts for oxidative degradation of Orange II dye in water. ZnO and MnO₂ were treated with 0.5, 0.75, or 1.0 N aqueous H₂SO₄. The acid treated oxides were found to be highly effective in bringing about degradation of Orange II in water. As much as 68.7% of the dye in an aqueous solution of 1 mg/L concentration could be degraded with untreated ZnO as the catalyst. The degradation increased to 79.5% with 1.0 N acid treated ZnO as the catalyst when the reaction was carried out at room temperature for 240 min. The catalytic activity was slightly affected by the solution pH in the range of 2.0–8.0. With MnO₂ as the catalyst, there was only 12.7% degradation of the dye, but this increased up to 100% when 0.5 N acid treated MnO₂ was used as the catalyst. It was found that a catalyst loading of 5.0 g/L of raw and acid‐treated ZnO and a loading of 0.5 g/L of raw and acid‐treated MnO₂ could bring about almost 100% degradation of Orange II in water in an interaction time of 240 min at room temperature.     

Role of container vessels in the introduction of exotic species

Ballast water exchange practices were monitored on 28 incoming container vessels at the Port of Montreal. Measurements on 15 vessels indicated 13 of 32 tanks had salinities of <30 per thousand. The 16 transits with a North Atlantic route visited 31 of 37 ports located on freshwater or near freshwater outflows. Ballast carried by this vessel type represents an important means for the introduction of species on a global scale because of its transit routes, dockside discharge and moving ballast between tanks. Container vessels represent about 15% of the world fleet, but account for 32% of all visits to global ports, and 46% of visits to the 25 largest ports. The 10 ports that handled the largest volumes of international cargo also included 8 that handled the most cargo containers. Large ports can receive over 100,000 visits by all vessel types annually, and serve as hubs for over 500 ports in 100 countries. Secondary transport of exotic species is also a concern because of frequent visits by regional vessels.     

Copper and sewage inputs from recreational vessels at popular anchor sites in a semi-enclosed Bay (Qld,Australia): Estimates of potential annual loads

Environmental impacts of vessels are well documented; Cu pollution as result of Cu based antifouling paints and nutrient pollution (such as N) from marine sewage are two examples of such disturbances. Understanding environmental impacts as well as the use of coastal waterways by recreational vessels is of concern to regulatory authorities, waterway users and local residents. In this study more than 55 aerial surveys were conducted of selected popular anchorages in eastern Moreton Bay, Queensland, Australia. Numbers of recreational vessels at certain times during the year were used in multiple linear regression analyses to develop predictive models for recreational vessel numbers. Over one year approximately 10,000 locally registered recreational craft (>6 m length overall) generated an estimated 59,000 vessel nights. With Cu leaching rates from the literature, and estimates of sewage inputs (assuming little or no use of pump-out facilities), load estimates associated with overnight use of 20 popular anchor sites were calculated as 141 ± 46 kg of Cu and 1.17 ± 0.38 t of nitrogen (N) annually. More importantly, the models showed vessel activity to be highly variable, and focused at peak holiday times, with 14% of vessel activity and associated pollutant loads entering the environment during Christmas and Easter. This study highlighted the inherent difficulties in managing a popular maritime amenity and Marine Parks such as the Moreton Bay Marine Protected Area, Queensland, Australia with its variety of stakeholders and types and intensities of uses.     

Photocatalytic degradation of spill oils on TiO2 nanotube thin films

The nitrogen-doped TiO₂ nanotube (N-TNT) thin films were synthesized using ZnO nanorods as the template and doped with urea at 623 K. Under ultraviolet (UV) and visible light irradiation, the efficiencies for photocatalytic degradation of methylene blue is as high as 30%. About 10% of toluene (representing aromatics in the spill oils) in sea water can be photocatalytically degraded under visible light radiation for 120 min. The aliphatic model compound (1-hexadecene) has, on the contrary, a less efficiency (8%) on the N-TNT photocatalyst. On the average, under visible light radiation, the effectnesses of the N-TNT for photocatalytic degradation of model compounds in the spill oils in sea water are 0.38 mg toluene/gN-TNT h and 0.25 mg 1-hexadecene/gN-TNT h. It is expected that spill oils in the harbors or seashores can be adsorbed and photocatalytically degraded on the N-TNT thin films that are coated onto levee at the sea water surface level.     

Potential ramifications of the global economic crisis on human-mediated dispersal of marine non-indigenous species

The global economy is currently experiencing one of its biggest contractions on record. A sharp decline in global imports and exports since 2008 has affected global merchant vessel traffic, the principal mode of bulk commodity transport around the world. During the first quarter of 2009, 10% and 25% of global container and refrigerated vessels, respectively, were reported to be unemployed. A large proportion of these vessels are lying idle at anchor in the coastal waters of South East Asia, sometimes for periods of greater than 3 months. Whilst at anchor, the hulls of such vessels will develop diverse and extensive assemblages of marine biofouling species. Once back in service, these vessels are at risk of transporting higher-than-normal quantities of marine organisms between their respective global trading ports. We discuss the potential ramifications of the global economic crisis on the spread of marine non-indigenous species via global commercial shipping.     

Degradation of Textile Dyeing Wastewater by a Modified Solar Photo‐Fenton Process Using Steel Scrap/H2O2

This experimental research deals with using steel scrap as a heterogeneous catalyst. This catalyzes the oxidation reaction of real textile dye wastewater based on a modified solar photo‐Fenton oxidation process. Morphologic analysis and mapping of the elementary composition of the steel scrap have been carried out by scanning electron microscopy. The effects of concentration of H₂O₂, the pH of the solution and the catalyst loading on the degradation of textile dye wastewater are elucidated. Kinetic studies have been performed for the decolorization of wastewater under optimum conditions. It could be concluded that the steel scrap is a potential substitute for ferrous salts as a catalyst for the solar photo‐Fenton reaction.     

Degradation of Aqueous Atrazine and Metazachlor Solutions by UV and UV/H2O2 — Influence of pH and Herbicide Concentration Abbau von Atrazin und Metazachlor in wäßriger Lösung durch UV und UV/H2O2 — Einfluß von pH und Herbizid-Konzentration

The degradation of two pesticides: atrazine and metazachlor was investigated in aqueous solution under UV-irradiation with and without H₂O₂. Rate constants of the photochemical degradation were determined applying a first order kinetics and quantum yields of the processes were calculated. This approach leads to an apparent decrease of the quantum yield with increasing initial pesticide concentration. At low H₂O₂ initial concentrations, the pesticide degradation was shown to be much more efficient than the degradation under UV-irradiation only. However, at high H₂O₂ concentrations (>2 mmol L^?1), the efficiency of the UV/H₂O₂ system dropped down and the quantum yields of degradation were lower than for the direct photolysis. In the absence of H₂O₂, no influence of the pH value on the photodegradation of the pesticides could be noticed in a range between pH 3 and pH 11. At low H₂O₂ initial concentrations, the photochemical degradation of the pesticides was much faster at pH 3 and pH 7 compared with the degradation at pH 11. The results emphasize the potential of optimized reaction conditions in advanced oxidation.     

Photochemical Degradation of Hydrophilic Xenobiotics in the UV/H2O2-process. Influence of Humic Matter on the Degradation Rate of 2-Amino-1-naphthalenesulfonate and Ethylenediaminetetraacetate

Photochemical oxidation methods are able to eliminate hydrophilic xenobiotics with a high efficiency. In waters with high DOC values caused by humic substances (HS) which are able to absorb UV light, problems can result. The degradation rates of the micropollutants using irradiation wavelengths in the range between λ = 200 nm to λ = 260 nm are significantly influenced by HS. This is mainly caused by the high absorption of the HS at shorter wavelength. In the presence of HS, the photolytic degradation of EDTA and FeEDTA was slowed down by an inner filter effect. A similar tendency could be seen for the photolytic degradation of 2-amino-1-naphthalenesulfonate where additional effects to the inner filter effect were also operating. In the UV/H₂O₂-process, the decrease of the degradation rate could be assigned to the ability of the HS to scavenge HO radicals.     

Electrical conductivity measurements on synthetic olivines and on olivine,enstatite and diopside from Dreiser Weiher,Eifel (Germany) under defined thermodynamic activities as a function of temperature and pressure

Results of electrical conductivity measurments on synthetic olivines of the system Mg₂SiO₄Fe₂SiO₄ and on minerals of Dreiser Weiher peridotite nodule Ib-8 (Eifel, Germany) are discussed in relation to the measuring procedure and to the variation of thermodynamic parameters.The measurements were performed in solid state high-pressure vessels between 340 and 1100°C and at a pressure of 10 kbar. It is shown that for ternary olivines and for pyroxenes, the control of two further variables, like the chemical activities of the components, is needed besides temperature and pressure control. The experimental set-up for the control of chemical activities and oxygen partial pressure is shown. From the slopes of the lines of log σ against 1/T the activation energies were calculated. Though in most cases the same oxygen fugacity ?_O2 is applied, the results reveal different values for synthetic and natural samples since the chemical activities of SiO₂ are different.     

Functioning of intertidal flats inferred from temporal and spatial dynamics of O<Subscript>2</Subscript>, H<Subscript>2</Subscript>S and pH in their surface sediment

In this article, we describe the dynamics of pH, O₂ and H₂S in the top 5–10 cm of an intertidal flat consisting of permeable sand. These dynamics were measured at the low water line and higher up the flat and during several seasons. Together with pore water nutrient data, the dynamics confirm that two types of transport act as driving forces for the cycling of elements (Billerbeck et al. 2006b): Fast surface dynamics of pore water chemistry occur only during inundation. Thus, they must be driven by hydraulics (tidal and wave action) and are highly dependent on weather conditions. This was demonstrated clearly by quick variation in oxygen penetration depth: Seeps are active at low tide only, indicating that the pore water flow in them is driven by a pressure head developing at low tide. The seeps are fed by slow transport of pore water over long distances in the deeper sediment. In the seeps, high concentrations of degradation products such as nutrients and sulphide were found, showing them to be the outlets of deep-seated degradation processes. The degradation products appear toxic for bioturbating/bioirrigating organisms, as a consequence of which, these were absent in the wider seep areas. These two mechanisms driving advection determine oxygen dynamics in these flats, whereas bioirrigation plays a minor role. The deep circulation causes a characteristic distribution of strongly reduced pore water near the low water line and rather more oxidised sediments in the centre of the flats. The two combined transport phenomena determine the fluxes of solutes and gases from the sediment to the surface water and in this way create specific niches for various types of microorganisms.     

Analysis of recent vessel arrivals and ballast water discharge in Alaska: toward assessing ship-mediated invasion risk

Ships are a dominant vector for biological invasions through ballast water discharge (BWD) and hull fouling. Here, we provide a first comprehensive analysis of shipping in Alaska, summarizing (a) the number, type and origin of vessel arrivals to Alaska for 2003 and 2004, (b) the spatial and temporal variation in vessel traffic, and (c) the available data on ballast water discharge in order to prioritize locations for tracking biological invasions. Most arrivals were passenger vessels, followed by ferries and fishing vessels, all of which carried little ballast water. Regional and seasonal patterns in arrivals and BWD were unevenly distributed among vessel types. The majority of vessels reporting BWD were from foreign ports, and most of this ballast was untreated. The largest volumes of ballast were from tankers at Valdez and Kenai Peninsula ports. Although Alaska has few documented invasions, opportunities for ship-mediated transfer now appear high and warrant further scrutiny.     

Stabilization Ponds Design as a function of Organic Removal Coefficient (K1)

The effluent from biological treatment plants of cane sugar factories undergoes a final purification in laboratory models with a Chlorella culture at volume loads of 76… 325 mg/l. d BOD₅ or 121… 555 mg/l-d COD. The coefficient of removal on the basis of BOD₅ is found to be linearly negatively correlated with the retention time, but independent of the substrate concentration and composition as well as of the pre-treatment of the wastewaters (aerobic or anaerobic). A dimensioning on the basis of the COD is not possible because of the high phytoplankton content in the effluent of the ponds.     

Photochemical Degradation of Hydrophilic Xenobiotics in the UV/H2O2-process. Influence of Bicarbonate on the Degradation Rate of EDTA, 2-Amino-1-naphthalenesulfonate,Diphenyl-4-sulfonate,and 4,4′-Diaminostilbene-2,2′-disulfonate

Hydrophilic xenobiotics can be eliminated in the UV/H₂O₂-process. The oxidation in this process is enhanced by the photolytically generated HO radicals. Bicarbonate is able to scavenge HO radicals. So it was expected that the degradation rates of the investigated xenobiotics were affected by the influence of bicarbonate. In contrast to the widely described decrease of the degradation rate, a much more complex situation was found in this investigation. The degradation rates of 2-amino-1-naphthalenesulfonate and diphenyl-4-sulfonate were decreased and reached for high concentrations of bicarbonate the values of the photolytical degradation rate. The degradation of 4,4′-diaminostilbene-2,2′-disulfonate was accelerated significantly in the presence of bicarbonate. The degradation rate of EDTA was increased at small concentrations of bicarbonate and decreased at higher concentrations.     

Monochloramination of Oxytetracycline: Kinetics,Mechanisms, Pathways,and Disinfection By‐Products Formation

This study investigated the degradation kinetics, formation of disinfection by‐products (DBPs), and degradation pathways during monochloramination of oxytetracycline (OTC). The degradation kinetics can be well described by a second‐order kinetic model, first‐order in monochloramine (NH₂Cl), and first‐order in OTC. Reaction of OTC with NH₂Cl shows a high reactivity, with the apparent rate constant of 17.64/M/s at pH 7. The apparent rate constant declined as pH increased from 5 to 10. Six DBPs were detected during monochloramination of OTC, including chloroform (CF), 1,1‐dichloro‐2‐propanone (1,1‐DCP), 1,1,1‐trichloro‐2‐propanone (1,1,1‐TCP), dichloroacetonitrile (DCAN), trichloronitromethane (TCNM), and N‐nitrosodimethlyamine (NDMA). CF, DCAN and NDMA had the maximum yields at neutral pH, while 1,1‐DCP and 1,1,1‐TCP had the maximum yields at pH 4. However, TCNM concentration increased as pH increased. Degradation pathways of OTC monochloramination were then proposed. Hydroxylation and Cl‐substitution are found to be the dominant mechanisms in monochloramination of OTC.