Recovery from eutrophication: experiences of reduced phosphorus input to the four largest lakes of Sweden

In-lake concentration changes of phosphorus (P) and nitrogen (N) in lakes V?ttern, V?nern, M?laren, and Hj?lmaren in response to diminished input has been examined from the mid-1960s onwards. In the former two deep and oligotrophic lakes with slow water renewal, drastic reductions in P-input from the middle of 1970s caused just minor reductions in P-concentration over a very long time. At the same time accumulation occurred in the water mass of inorganic N and possible reasons are discussed. In the latter two mesotrophic to hypertrophic lakes, two shallow basins in L. Hj?lmaren showed slow recovery due to release of P from sediments. The same basins and two basins in L. M?laren have suffered from N-deficiency, particularly during the pre-phosphorus reduction years, and nitrogen fixation was indicated. In two L. M?laren basins recovery of in-lake P concentrations was better than expected in comparison to the so-called IMSA-model for lake recovery from nutrient pollution. In the other five lakes/basins chlorophyll concentrations after 20 years were similar compared to those modeled.     

Determination of airborne anhydrides using LC-MS monitoring negative ions of di-n-butylamine derivatives

An air sampling method for simultaneous determination of organic acid anhydrides and isocyanates is presented. Air samples are collected in impinger flasks filled with 0.01 M di-n-butylamine (DBA) in a mixture of toluene-acetonitrile (7:3, v/v) with a 13 millimetre glass fibre filter in series. The amount of anhydrides and isocyanates are determined as their amide and urea derivatives using LC-MS. Four anhydrides, maleic anhydride (MA), phthalic anhydride (PA), tetrahydrophthalic anhydride (TA) and cis-hexahydrophthalic anhydride (HA) and 11 isocyanates could be separated in 9 minutes using gradient elution. Anhydride-DBA derivatives in standard solutions were quantified using LC with chemiluminescent nitrogen detection (CLND). Anhydride-DBA derivatives were found to be stable for at least two months when stored in acetonitrile or toluene in the freezer. The yield of DBA derivatives of anhydrides in the 0.01 M DBA in toluene-acetonitrile (7:3, v/v) was in the range of 70->95%. Using MS and negative electrospray ionisation (ES-) linear calibrations curves were obtained for the anhydrides with correlation coefficients ranging from 0.9970-0.9997. The instrumental detection limit for the anhydrides ranged from 10-30 fmol, based on a signal to noise root mean square (RMS) ratio of 3. Monitoring positive and negative ions simultaneously, both isocyanates and anhydrides could be determined as their DBA derivatives in the same chromatographic run. When air samples were collected during thermal degradation of different coated metal sheets both anhydrides and isocyanates were present in the same samples and all the studied anhydrides were found.     

Determination of technical grade isocyanates used in the production of polyurethane plastics

A method for determination of technical grade isocyanates used in the production of polyurethane (PUR) is presented. The isocyanates in technical grade products were characterised as di-n-butylamine (DBA) derivatives using LC-MS and LC-chemiluminescent nitrogen detection (CLND) and the total isocyanate content was compared to a titration assay. For collection of isocyanates in air, an impinger-filter sampling technique with DBA as derivatisation reagent was used. Characterised DBA and nonadeuterium labelled DBA derivatives of isocyanates in technical products were used as calibration standards and internal standards, respectively, in the analysis of air samples. Three workplaces were studied where PUR products were produced either by spraying or by moulding. In both technical products and in air samples, a number of monomeric, oligomeric and prepolymeric isocyanates of e.g. methylenebisphenyl diisocyanate (MDI) and hexamethylene diisocyanate (HDI) were characterised. Several of these have not previously been described in workplace atmospheres. In the technical isocyanate products, between 69 and 102% of the NCO content determined by titration was accounted for by LC-CLND. Quantifications of a wide range of isocyanates in air samples were performed with correlation coefficients in the range 0.988-0.999 (n= 8) and the instrumental detection limits were 0.7-25 pg. At the two workplaces where MDI- and HDI isocyanurate-based products were sprayed, the isocyanate composition in the air reflected the composition in the technical product. At the workplace where a MDI-based product was used in a moulding process, only the monomeric isocyanates were found in the air. The advantage of using characterised technical grade isocyanates as analytical standards was clearly demonstrated and the possibility of using index compounds when monitoring isocyanate exposure is discussed.     

Determination of isocyanates, aminoisocyanates and amines in air formed during the thermal degradation of polyurethane

An air sampling method for the determination of isocyanates, aminoisocyanates and amines formed during the thermal degradation of polyurethane (PUR) is presented. The method is based on the collection of air samples using impinger flasks containing di-n-butylamine (DBA) in toluene with a glass fibre filter in series. Isocyanates are derivatized with DBA to urea derivatives, and amines are derivatized in a subsequent work-up procedure with ethyl chloroformate (ET) to carbamate esters. Amine, aminoisocyanate and isocyanate derivatives were characterized using liquid chromatography-time of flight mass spectrometry (LC-TOFMS) and liquid chromatography-chemiluminescent nitrogen detection (LC-CLND). Quantification was performed by LC-MS, monitoring molecular ions [MH]+ in the electrospray mode. The instrumental detection limits for amines, aminoisocyanates and isocyanates were in the ranges 30-40, 2-3 and 3-70 fmol, respectively. Thermal degradation products of PUR were observed in high concentrations during welding in district heating pipes and PUR-coated metal sheets. Eleven isocyanates, three amines and five aminoisocyanates were identified. The concentrations of isocyanates, aminoisocyanates and amines in samples collected in the smoke close to the welding spot were in the ranges 150-650, 4-290 and 1-70 ppb, respectively. In samples collected in the breathing zone, isocyanates and aminoisocyanates were observed in the ranges 9-120 and 4-19 ppb, respectively. The compounds were present in both gas and particle phases. Volatile compounds dominated in the gas phase, whereas less volatile compounds dominated in the particle phase. The method presented makes it possible to sample and determine amines and aminoisocyanates, in addition to isocyanates. The need to monitor these compounds is clearly illustrated by the high concentrations found during the thermal degradation of PUR.     

Tracing recovery from acidification in the western Norwegian Nausta watershed

A novel method, redundancy analysis (RDA), has been used to examine whether chemical recovery from acidification in the western Norwegian Nausta watershed produces detectable recovery within the community structure of the macro-zoobenthos. The RDA results have been compared with measures of recovery based on the changes detected using highly specialized and regionally defined biological acidity indices. We found that the beginning of biological recovery in the Nausta watershed was recognizable during the period 1989-1998. Recovery occurred in the upper reaches and in the tributaries. The multivariate approach proved to complement the acidity indices approach, and much biological information can be gained by their combined use. The RDA method is conservative, i.e. does not overestimate biological recovery, and it is not geographically constrained as are the acidity indices. We also found that seasonal climatic factors strongly influence the benthic community, and may confound the detection of the biological recovery process.     

Comparative health impact assessment of local and regional particulate air pollutants in Scandinavia

The ongoing program Clean Air for Europe (CAFE) is an initiative from the EU Commission to establish a coordinated effort to reach better air quality in the EU. The focus is on particulate matter as it has been shown to have large impact on human health. CAFE requested that WHO make a review of the latest findings on air pollutants and health to facilitate assessments of the different air pollutants and their health effects. The WHO review project on health aspects of air pollution in Europe confirmed that exposure to particulate matter (PM), despite the lower levels we face today, still poses a significant risk to human health. Using the recommended uniform risk coefficients for health impact assessment of PM, regardless of sources, premature mortality related to long-range transported anthropogenic particles has been estimated to be about 3500 deaths per year for the Swedish population, corresponding to a reduction in life expectancy of up to about seven months. The influence of local sources is more difficult to estimate due to large uncertainties when linking available risk coefficients to exposure data, but the estimates indicate about 1800 deaths brought forward each year with a life expectancy reduction of about 2-3 months. However, some sectors of the population are exposed to quite high locally induced concentrations and are likely to suffer excessive reductions in life expectancy. Since the literature increasingly supports assumptions that combustion related particles are associated with higher relative risks, further studies may shift the focus for abatement strategies. CAFE sets out to establish a general cost effective abatement strategy for atmospheric particles. Our results, based on studies of background exposure, show that long-range transported sulfate rich particles dominate the health effects of PM in Sweden. The same results would be found for the whole of Scandinavia and many countries influenced by transboundary air pollution. However, several health studies, including epidemiological studies with a finer spatial resolution, indicate that engine exhaust particles are more damaging to health than other particles. These contradictory findings must be understood and source specific risk estimates have to be established by expert bodies, otherwise it will not be possible to find the most cost effective abatement strategy for Europe. We are not happy with today's situation where every strategy to reduce PM concentrations is estimated to have the same impact per unit change in the mass concentration. Obviously there is a striking need to introduce more specific exposure variables and a higher geographical resolution in epidemiology as well as in health impact assessments.     

Die Kristallstruktur des monoklinen α-Bi2O3

The Science of Nature -     

Effects of small-scale habitat fragmentation on predator–prey interactions in a temperate sea grass system

During the last decades, fragmentation has become an important issue in ecological research. Habitat fragmentation operates on spatial scales ranging over several magnitudes from patches to landscapes. We focus on small-scale fragmentation effects relevant to animal foraging decision making that could ultimately generate distribution patterns. In a controlled experimental environment, we tested small-scale fragmentation effects in artificial sea grass on the feeding behaviour of juvenile cod (Gadus morhua). Moreover, we examined the influence of fragmentation on the distribution of one of the juvenile cod’s main prey resources, the grass shrimp (Palaemon elegans), in association with three levels of risk provided by cod (no cod, cod chemical cues and actively foraging cod). Time spent by cod within sea grass was lower in fragmented landscapes, but total shrimp consumption was not affected. Shrimp utilised vegetation to a greater extent in fragmented treatments in combination with active predation. We suggest that shrimp choose between sand and vegetation habitats to minimize risk of predation according to cod habitat-specific foraging capacities, while cod aim to maximize prey-dependent foraging rates, generating a habitat-choice game between predator and prey. Moreover, aggregating behaviour in grass shrimp was only found in treatments with active predation. Hence, we argue that both aggregation and vegetation use are anti-predator defence strategies applied by shrimp. We therefore stress the importance of considering small-scale behavioural mechanisms when evaluating consequences from habitat fragmentation on trophic processes in coastal environments.     

Molecular effects and bioaccumulation of levonorgestrel in the non-target organism Dreissena polymorpha

Bioaccumulation and effects of the contraceptive hormone levonorgestrel were examined in the non-target organism Dreissena polymorpha. Molecular biomarkers of biotransformation, elimination, antioxidant defence and protein damage were analyzed after exposure to increasing concentrations of levonorgestrel in a flow-through system. The lowest concentration (0.312 μg L⁻¹) was 100-fold bioconcentrated within four days. A decrease of the bioconcentration factor was observed within one week for the highest test concentrations (3.12 and 6.24 μg L⁻¹) suggesting enhanced excretory processes. The immediate mRNA up-regulation of pi class glutathione S-transferase proved that phase II biotransformation processes were induced. Disturbance of fundamental cell functions was assumed since the aryl hydrocarbon receptor has been permanently down-regulated. mRNA up-regulation of P-glycoprotein, superoxide dismutase and metallothioneine suggested enhanced elimination processes and ongoing oxidative stress. mRNA up-regulation of heat shock protein 70 in mussels exposed to the two highest concentrations clearly indicated impacts on protein damage.