Modeling riverine nutrient transport to the Baltic Sea: a large-scale approach

We developed for the first time a catchment model simulating simultaneously the nutrient land-sea fluxes from all 105 major watersheds within the Baltic Sea drainage area. A consistent modeling approach to all these major watersheds, i.e., a consistent handling of water fluxes (hydrological simulations) and loading functions (emission data), will facilitate a comparison of riverine nutrient transport between Baltic Sea subbasins that differ substantially. Hot spots of riverine emissions, such as from the rivers Vistula, Oder, and Daugava or from the Danish coast, can be easily demonstrated and the comparison between these hot spots, and the relatively unperturbed rivers in the northern catchments show decisionmakers where remedial actions are most effective to improve the environmental state of the Baltic Sea, and, secondly, what percentage reduction of riverine nutrient loads is possible. The relative difference between measured and simulated fluxes during the validation period was generally small. The cumulative deviation (i.e., relative bias) [Sigma(Simulated - Measured)/Sigma Measured x 100 (%)] from monitored water and nutrient fluxes amounted to +8.2% for runoff, to -2.4% for dissolved inorganic nitrogen, to +5.1% for total nitrogen, to +13% for dissolved inorganic phosphorus and to +19% for total phosphorus. Moreover, the model suggests that point sources for total phosphorus compiled by existing pollution load compilations are underestimated because of inconsistencies in calculating effluent loads from municipalities.     

Value of information analysis in remedial investigations

Site investigations of contaminated land are associated with high costs. From a societal perspective, just enough economic resources should be spent on investigations so that society's limited resources can be used optimally. The solution is to design investigation programs that are cost effective, which can be performed using value of information analysis (VOIA). The principle of VOIA is to compare the benefit at the present state of knowledge with the benefit that is expected after an investigation has been performed. A framework for VOIA of site investigations is presented based on Bayesian risk-cost-benefit decision analysis. The result is an estimate of the value of an investigation program and, for specific problems, the optimal number of samples. The main strength of the methodology is that it promotes clear thinking and compels the decision maker to reflect on issues that otherwise would be ignored. The main weakness is the complexity of VOIA models.     

Molecular orbital studies on brominated diphenyl ethers. Part I--conformational properties

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants and quantities in the environment are on the rise. Because they are structurally related to polychlorinated biphenyls and also to thyroid hormones, there is serious concern that PBDEs may pose a danger to human health. Knowledge of their conformational properties is key to assessing their environmental fate and risk. The conformational properties of PBDEs were investigated by quantum chemical methods including semiempirical self-consistent field molecular orbital (SCF-MO), ab initio SCF-MO and density functional theory (DFT). Conformational analyses of model congeners 2,2',4,6'-tetrabromodiphenyl ether and 2,3,4,4',5,6-hexabromodiphenyl ether, based on energy maps calculated by semiempirical AM1 method, may indicate that all PBDE congeners except those with the tetra-ortho-bromination are conformationally flexible (or soft) due to low energy barriers for interconversion of stable conformers. The results of the conformational analyses are in conformity with recently published X-ray crystallographic data. For comparison with the results of the semiempirical method, higher level ab initio and DFT models were applied as well. The optimized geometries all lie well inside low energy regions on the maps and thus also ascertain the semiempirical calculations. According to computed geometric parameters and net atomic charges, the model B3LYP/3-21G* seemed to give better results than B3LYP/6-31G* and HF/6-31G*.     

Molecular orbital studies on brominated diphenyl ethers. Part II--reactivity and quantitative structure-activity (property) relationships

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and are increasingly turning up in the environment. Their structural similarities to polychlorinated biphenyls and thyroid hormones suggest they may be a risk to human health. The present study examines the reactivity of brominated diphenyl ethers (BDEs) on the basis of the electronic structures as calculated by semiempirical AM1 self-consistent field molecular orbital (SCF-MO) method. Frontier orbital energies were used to elucidate the reactivity of BDEs in electrophilic, nucleophilic and photolytic reactions. From an examination of the frontier electron densities, the regioselectivity, or orientation, of metabolic reactions of BDEs was predicted. Furthermore, satisfactory quantitative structure-activity (property) relationship (QSAR and QSPR) models were derived to calculate gas chromatographic and ultraviolet spectral properties and luciferase induction activities from the AM1-computed electronic parameters.     

Biodegradation rates in adapted surface water can be assessed following a preadaptation period with semi-continuous operation

The paper presents a semi-continuous preexposure procedure (SCEP) for use with surface water batch simulation biodegradability tests at low test substance concentrations (0.1-100 microg/l). Simple one step batch tests are normally used first of all for determining "initial rates" characteristic of the water as sampled, as by contrast to "adapted" rates obtained as a result of exposure of the microbial community to the test compound. The aim of the SCEP is to facilitate this adaptation and to become able to estimate reproducible "adapted rates" representing a steady state situation. This is accomplished by maintaining the microbial diversity and a supply of test substance and natural substrates. Conducting a SCEP involves regular renewal of part (e.g. one third) of the test suspension (e.g. every two weeks) adding freshly collected natural water with test compound of the initial concentration. An example study was performed with aniline, 4-nitrophenol, 2,4-dichlorophenoxyacetic acid, 4-chloroaniline, and water from the urban river M?lle?. Following preadaptation lag phases were considerably reduced and much more reproducible than obtained with simple batch tests. In tests at 100 microg/l lag phases for aniline decreased from 5.2 to <1 day, 4-nitrophenol from 10 to <1 day, 2,4-dichlorophenoxyacetic acid from 24 to <1 day, and 4-chloroaniline from 88 to 9 days, respectively. Adapted rates obtained with the SCECP were roughly the same as final rates in simple batch tests with successful adaptation. The adapted rate constant is perceived as an inherent characteristic of the test compound at a specific concentration and under environmental influence (temperature, natural substrates, etc.) but with no simple links back to the original microbial population. By contrast, the initial rates in one step batch tests are determined also by the microbial population initially present in the water sampled.     

Experiences with unexpected structural chromosome aberrations in prenatal diagnosis in a danish series

The investigation of 5547 prenatal diagnoses showed 31 unexpected structural chromosome rearrangements. These included 3 Robertsonian translocations, 14 reciprocal translocations and 14 inversions. A11 were balanced, including 5 de novo rearrangements. In 3 of these cases an induced abortion was performed and in 2 cases children without detectable malformations were delivered.     

Leaching and crop uptake of nitrogen from nitrogen-15-labeled green manures and ammonium nitrate

Green manures can be used as an N source for agricultural crops as a substitute for inorganic N fertilizers. The effects of using green manures on leaching and uptake of N by spring barley (Hordeum vulgare L.) were evaluated in a 2-yr lysimeter study. Ryegrass (Lolium perenne L.) and red clover (Trifolium pratense L.) labeled with (15)N were applied in May of the first year at 160 kg total N ha(-1). Simultaneously, (15)NH(4)(15)NO(3) was applied at 80 kg N ha(-1) to additional lysimeters and others were left without N additions (control). During the second year, all lysimeters, except the control, received 80 kg N ha(-1) as unlabeled NH(4)NO(3). The cumulative, average loads of total N leached during the two years were: 37 (control), 62 (NH(4)NO(3)), 50 (ryegrass manure), and 73 (red clover manure) kg ha(-1). The differences among the treatments were not significant (P > 0.05), but the control had significantly smaller (P < 0.05) leaching loads than the treatments. About 24% of ryegrass- and red clover-derived N and 43% of NH(4)NO(3) were removed through spring barley grain and stover during the two growing seasons. Thus, the N use efficiency in barley was substantially larger when grown with inorganic N fertilizer than when grown with green manure. Viewed in combination with the tendency for larger N leaching loads under red clover manure, claims about water quality benefits of legume-based green manures should be evaluated with regard to the timing of N release and demand for N by the plant.     

Development of a rapid method for direct detection of tet(M) genes in soil from Danish farmland

A method for direct detection of antibiotic resistance genes in soil samples has been developed. The tetracycline resistance gene, tet(M), was used as a model. The method was validated on Danish farmland soil that had repeatedly been treated with pig manure slurry containing resistant bacteria. The tet(M) gene was directly detected in 10-80% of the samples from the various farmland soils and could be detected in all samples tested after selective enrichment. To validate the obtained results, the method was applied to garden soil samples where lower prevalence of resistance was found. RESULT: A detection limit of 10(2)-10(3) copies of the tet(M) gene per gram of soil (in a Bacillus cereus group bacterium) was achieved. tet(M) gene was detected in soil samples with the highest prevalence on farmland treated with pig manure slurry.     

Review and assessment of models for predicting the migration of radionuclides from catchments

The present paper summarises the results of the review and assessment of models developed for predicting the migration of radionuclides from catchments to water bodies. The models were classified and evaluated according to their main methodological approaches. A retrospective analysis of the principles underpinning the model development in relation to experimental finding and results was carried out. It was demonstrated that most of the various conceptual approaches of different modellers can be integrated in a general, harmonised perspective supported by a variety of experimental evidences. Shortcomings and advantages of the models were discussed.     

Presence of erm genes among macrolide-resistant Gram-positive bacteria isolated from Danish farm soil

The presence of erm genes was investigated among macrolide-resistant Gram-positive bacteria isolated from soil samples collected from four Danish farms that had been treated with animal waste. Soil samples were collected before, a few days after spread and 1 1/2 months and 5 months later. In 33% (9/27) of these isolates, an erm gene was detected using PCR. Eight isolates were positive for erm(B) and one isolate was positive for erm(C). No isolates contained erm(A), erm(D) or erm(F). The positive isolates were identified to genus level. Two erm(B) positive isolates were identified as Enterococcus spp., and the erm(C)-positive isolate as a Streptococcus spp., probably indicating survival from animal waste. The remaining six erm(B) positive isolates all belonged to the Bacillus cereus group. The erm(B) gene has not previously been identified in B. cereus but is frequently found among enterococci. This result could indicate horizontal transfer from bacteria of animal origin to indigenous soil bacteria.