Relationship between release of nitric oxide and CO2 and their dependence on oxidation reduction potential in wastewater treatment

Nitric oxide (NO) is an intermediate of denitrification process and can be produced by denitrifiers, nitrifiers and other bacteria. In our experiments we measured the dynamic flow of NO depending on oxidation reduction potential (ORP). Different ORP-ranges were related to various carbon loading stages in the wastewater treatment pilot plant. Nitrification and denitrification were achieved by a sequence of aeration and non-aeration periods. Our measurements show that different carbon loading conditions (low feed, balanced and overloaded conditions) did not change the range of the mixing ratio of NO emissions when the aeration conditions like air-flow and temperature were kept constant. Minimum and maximum NO mixing ratios were 34.7 and 91.8 ppbv; 52.3 and 91.3 ppbv; 57.6 and 109 ppbv for low feed, balanced and overloaded conditions, respectively. The curve of the NO graph relied on nitrification/denitrification dynamics. The dependence of NO release on different ORP and CO2-release during the various conditions are shown. Longer aeration times resulted in an increased release of gaseous NO. The net-release of NO g(-1) nitrogen removed was between 0.014% and 0.028%. The NO fluxes to the air were observed between 8.3 and 14.9 mg m(-2) d(-1) NO. The major release occurred during high aeration periods whereas the concentration of dissolved [NOaq] in the wastewater was less than 0.05% of the gaseous release due to very low solubility of the NO.     

Reactive transport modeling of processes controlling the distribution and natural attenuation of phenolic compounds in a deep sandstone aquifer

Reactive solute transport modeling was utilized to evaluate the potential for natural attenuation of a contaminant plume containing phenolic compounds at a chemical producer in the West Midlands, UK. The reactive transport simulations consider microbially mediated biodegradation of the phenolic compounds (phenols, cresols, and xylenols) by multiple electron acceptors. Inorganic reactions including hydrolysis, aqueous complexation, dissolution of primary minerals, formation of secondary mineral phases, and ion exchange are considered. One-dimensional (1D) and three-dimensional (3D) simulations were conducted. Mass balance calculations indicate that biodegradation in the saturated zone has degraded approximately 1-5% of the organic contaminant plume over a time period of 47 years. Simulations indicate that denitrification is the most significant degradation process, accounting for approximately 50% of the organic contaminant removal, followed by sulfate reduction and fermentation reactions, each contributing 15-20%. Aerobic respiration accounts for less than 10% of the observed contaminant removal in the saturated zone. Although concentrations of Fe(III) and Mn(IV) mineral phases are high in the aquifer sediment, reductive dissolution is limited, producing only 5% of the observed mass loss. Mass balance calculations suggest that no more than 20-25% of the observed total inorganic carbon (TIC) was generated from biodegradation reactions in the saturated zone. Simulations indicate that aerobic biodegradation in the unsaturated zone, before the contaminant entered the aquifer, may have produced the majority of the TIC observed in the plume. Because long-term degradation is limited to processes within the saturated zone, use of observed TIC concentrations to predict the future natural attenuation may overestimate contaminant degradation by a factor of 4-5.     

Environmental effects of one thousand years of copper production at Falun, central Sweden

Copper production in Falun, central Sweden, has emitted sulfur dioxide (SO2) and metals to the air during at least 1000 years. Emissions peaked in the 17th century when Falun produced 2/3 of the world's copper supply. This area offers unique opportunities to study long-term effects of acid deposition and metal pollution, including recovery following the three centuries of decreasing SO2 and metal deposition. Here we present a 1000-yr perspective on local emissions of SO2, estimated air concentrations and dry deposition of SO2, as well as results on acidification and metal pollution of soils and lakes. Despite a long period when deposition of SO2 exceeded the critical load, soil acidification is limited to the most heavily polluted area 12 km NW and SE from the mine. According to diatom analyses of take sediments, only 8 of 14 lakes have become acidified (0.4-0.8 pH units). None of these lakes show recovery from acidification, probably due to large amounts of sulfate still accumulated in the soils and changes in land use.     

Decrease of PCDD/F levels in human blood from Germany over the past ten years (1989-1998)

744 whole blood samples of normal subjects from Germany collected in 1989-1998 have been analyzed for polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) by capillary gas chromatography/high resolution mass spectrometry. Over the examined time period a continuous decrease of the PCDD/F concentrations in human blood was observed. The mean levels found were 43.7 pg I-TEq/g (lipid basis) in 1989 and 20.7 pg I-TEq/g (lipid basis) in 1996/98 [median: 42.2 and 19.4]. The reduction to about the half was found for most congeners. Each one-year subset of the collective and the entire collective shows a positive correlation of the PCDD/F blood levels with age for most of the congeners, the sum values and the calculated toxicity equivalents. For statistical evaluation a multiplicative model was used: Concentration = A x Age(B). The correlation is mostly pronounced for lower chlorinated PCDD and for 2,3,4,7,8-PentaCDF. The PCDD/F concentrations in human blood in relation to the year of examination and the age of the subjects can be described by a linear model: I-TEq [pg/g (lipid basis)] = 6176 - 3.097 x Year + 0.6482 x Age or by a multiplicative model: I-TEq [pg/g(lipid basis)] = 10(89.08-0.04415 x Year + 0.008468 x Age).     

Priority assessment of toxic substances in life cycle assessment. Part I: calculation of toxicity potentials for 181 substances with the nested multi-media fate, exposure and effects model USES-LCA

Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. In most cases, toxicity potentials are calculated with multi-media fate models. Until now, unrealistic system settings were used for these calculations. The present paper outlines an improved model to calculate toxicity potentials: the global nested multi-media fate, exposure and effects model USES-LCA. It is based on the Uniform System for the Evaluation of Substances 2.0 (USES 2.0). USES-LCA was used to calculate for 181 substances toxicity potentials for the six impact categories freshwater aquatic ecotoxicity, marine aquatic ecotoxicity, freshwater sediment ecotoxicity, marine sediment ecotoxicity, terrestrial ecotoxicity and human toxicity, after initial emission to the compartments air, freshwater, seawater, industrial soil and agricultural soil, respectively. Differences of several orders of magnitude were found between the new toxicity potentials and those calculated previously.     

The use of Littorina littorea for tributyltin (TBT) effect monitoring - Results from the German TBT survey 1994/1995 and laboratory experiments

Field investigations and laboratory experiments were performed to test the applicability of the intersex phenomenon in Littorina littorea for biological TBT-effect monitoring and to give further insights into toxicological aspects of intersex development. The intensity of the phenomenon is correlated with the degree of TBT contamination in the environment. Statistically highly significant correlations of biological indices and TBT concentrations in tissue and sediment exist. Intersex can be induced only in juvenile and sexually immature females and its intensity depends on the ontogenetic stage of development during TBT exposure. For the first time, malformations in male periwinkles closely related to the TBT contamination can be described; the reduction of male mamilliform penial glands shows highly significant correlations to TBT concentrations in tissues. The intersex phenomenon in Littorina littorea is proposed for a biological TBT-effect monitoring in those areas where the dogwhelk Nucella lapillus, as the more sensitive species in European surveys, is absent. The intersex index (ISI) as the mean value of the intersex stages in a sample should be used as the most sensitive biological parameter for the assessment of the TBT contamination in Littorina littorea.     

Modelling stomatal responses of spring wheat (Triticum aestivum L. cv. Turbo) to ozone and different levels of water supply

Spring wheat (Triticum aestivum L. cv. Turbo) was exposed to different levels of ozone and water supply in open-top chambers in 1991. Air was charcoal filtered (CF), non-filtered (NF) and CF plus proportional addition of ambient or twice ambient ozone (CF1, CF2). Seasonal means of O(3), taken over 24 h, were 2.3, 20.6, 17.3, and 34.5 nl litre(-1) for CF, NF, CF1 and CF2 treatments, respectively. A split-plot design was used to obtain two levels of water supply: one-half of the pots was irrigated sufficiently not to show any symptoms of drought stress; the others were exposed to low water supply and received 50% of these amounts. Using a steady-state porometer approximately 800 measurements of stomatal conductance (g(s)) were made on flag leaves from 68 to 106 days after sowing. The measurements yielded only small differences of maximum conductance between the two levels of water supply. Therefore, low water supply did not protect wheat plants against ozone injury via reduced stomatal uptake in this experiment. To describe the effects of environmental variables on the stomatal behaviour, boundary-line analysis and non-linear regression analysis were used. Besides microclimatic parameters, the ozone dose of flag leaves was introduced as an independent variable affecting stomatal aperture. A well-defined boundary line for ozone dose was found, suggesting that increasing ozone dose caused stomatal closure in wheat flag leaves. But at high ozone doses, co-acting senescence seems also responsible for the decrease in stomatal conductance. A multiplicative boundary-line model was used to predict stomatal conductance from combinations of environmental variables. In the test carried out with the measurements of stomatal conductance, the model accounted only for 40% of the variation of g(s). Generalized stomatal response patterns of the herbaceous growth form, the dependence of the variables' age and ozone dose and the lack of an important factor influencing stomatal response (water status of the plant) in the model, are suggested as explanations of the poor results of the test.     

Bioaccumulation of PCBs in Arctic seabirds: influence of dietary exposure and congener biotransformation

Four seabird species and their prey (zooplankton or fish) were collected in the Barents Sea to determine how dietary exposure, cytochrome P450 (CYP) enzyme activities and sex influenced their hepatic PCB concentrations and accumulation patterns. Five males and five females from each seabird species (little auk (Alle alle), Brunnich's guillemot (Uria lomvia), black guillemot (Cepphus grylle) and black-legged kittiwake (Rissa tridactyla)) were analysed. PCB concentrations could not be explained directly by carbon source (delta13C) or trophic position (delta15N), but by a combination of dietary parameters (delta13C, delta15N, migratory pattern, age) and contaminant metabolism. Contrary to previous studies, the PCB pattern differed among seabirds, with a higher proportion of persistent congeners (% of PCB-153, RPCB-153) in black-legged kittiwake than in auks. The PCB pattern also differed among auks, with little auk as the most efficient biotransformer (highest RPCB-153 values of persistent congeners). Based on high RPCB-153 values, Brunnich's guillemot poorly metabolised ortho-meta-unsubstituted congeners, whereas black guillemot poorly metabolised meta-para unsubstituted congeners. Species-specific differences in PCB biotransformation were confirmed by metabolic indices, where PCB patterns in seabirds were adjusted for PCB pattern in prey. The relative contribution of ortho-meta-unsubstituted congeners to SigmaPCBs decreased with increasing EROD activity. There were no differences in PCB concentrations, PCB patterns or cytochrome P450 enzyme activities between males and females. CYP P450 activities (CYP1A- and CYP2B/3A-like: EROD and testosterone 6beta-hydroxylation, respectively) were low and did not correlate with concentrations of non- or mono-ortho Cl-substituted PCBs (NO- and MO-PCBs), or with total toxic equivalent concentrations (TEQs) for dioxin-like effects of NO- and MO-PCBs.     

Comparison of organochlorine concentrations and patterns between free-ranging zooplankton and zooplankton sampled from seabirds' stomachs

To investigate the use of predators' stomach contents to measure the organochlorine load in free-ranging prey, the two zooplankton species Thysanoessa inermis (euphausiids) and Themisto libellula (amphipods) were collected simultaneously from the water column and from the seabird Brünnich's guillemot (Uria lomvia)'s stomach (from crop to proventriculus). The organochlorine compounds' concentrations and relative proportion of PCB-153 generally did not differ between the two sampling methods (least square mean of Sigma organochlorines=5.9 and 6.8 ng g(-1) wet weight for water column and stomach-sampled prey, respectively), indicating that the organochlorines in stomach-sampled prey were not yet affected by mechanical, chemical and bacterial degradation. Although the sample size is restricted, similar organochlorine concentrations and pattern in free-ranging and stomach-sampled prey may suggest that Brünnich's guillemots feed randomly on the zooplankton population rather than at more (or less) contaminated individuals. Alternatively or in addition, the similar concentrations and pattern suggest that the contaminant levels in Barents Sea zooplankton do not influence their behaviour to change the vulnerability to predation. In conclusion, the organochlorine concentrations and pattern in zooplankton collected from seabirds' stomach correspond with levels in free-ranging prey.     

Ammonia emission, deposition and impact assessment at the field scale: a case study of sub-grid spatial variability

A local ammonia (NH3) inventory for a 5x5 km area in central England was developed, to investigate the variability of emissions, deposition and impacts of NH3 at a field scale, as well as to assess the validity of the UK 5-km grid inventory. Input data were available for the study area for 1993 and 1996 on a field by field basis, allowing NH3 emissions to be calculated for each individual field, separately for livestock grazing, livestock housing and manure storage, landspreading of manures and fertiliser N application to crops and grassland. An existing atmospheric transport model was modified and applied to model air concentrations and deposition of NH3 at a fine spatial resolution (50 m grid). From the mapped deposition estimates and land cover information, critical loads and exceedances were derived. to study the implications of local variability for regional NH3 impacts assessments. The results show that the most extreme local variability in NH3 emissions, deposition and impacts is linked to housing and storage losses. However, landspreading of manures and intensive cattle grazing are other important area sources, which vary substantially in the landscape. Overall, the range of predicted emissions from agricultural land within the study area is 0-2000 kg N ha(-1) year(-1) in 1993 and 0-8000 kg N ha(-1) year(-1) in 1996, respectively, with the peak at a poultry farm located in the study area. On average, the estimated field level NH3 emissions over the study area closely match the emission for the equivalent 5-km grid square in the national inventory for 1996. Deposition and expected impacts are highly spatially variable, with the edges of woodland and small "islands" of semi-natural vegetation in intensive agricultural areas being most at risk from enhanced deposition. Conversely the centres of larger nature reserves receive less deposition than average. As a consequence of this local variability it is concluded that national assessments at the 5 km grid level underestimate the occurrence of critical loads exceedances due to NH3 in agricultural landscapes.