Validation and use of in vivo solid phase micro-extraction (SPME) for the detection of emerging contaminants in fish

A variety of emerging chemicals of concern are released continuously to surface water through the municipal wastewater effluent discharges. The ability to rapidly determine bioaccumulation of these contaminants in exposed fish without sacrificing the animal (i.e. in vivo) would be of significant advantage to facilitate research, assessment and monitoring of their risk to the environment. In this study, an in vivo solid phase micro-extraction (SPME) approach was developed and applied to the measurement of a variety of emerging contaminants (carbamazepine, naproxen, diclofenac, gemfibrozil, bisphenol A, fluoxetine, ibuprofen and atrazine) in fish. Our results indicated in vivo SPME was a potential alternative extraction technique for quantitative determination of contaminants in lab exposures and as well after exposure to two municipal wastewater effluents (MWWE), with a major advantage over conventional techniques due to its ability to non-lethally sample tissues of living organisms.     

Mean annual (222)Rn concentration in homes located in different geological regions of Poland: first approach to whole country area

The paper presents the results of year-long measurements of radon (²²²Rn) concentration inside 129 buildings in Poland in relation to the geological conditions of their foundation. The authors took into account the division of the country into tectonic units, as well as the lithology of the rocks forming the bedrock of these buildings. As expected, the highest value of mean annual ²²²Rn concentration (845 Bq/m³) was recorded in a building situated in the area of the Sudetes, while the highest geometric mean (characteristic of the expected log-normal data distribution) was calculated based on measurements from buildings located within the East-European craton, in the area of Mazury-Podlasie monocline, where it reached 231 Bq/m³. Such results reflect geological conditions - the occurrence of crystalline rocks (especially U- and Ra-enriched granites and orthogneisses) on the surface in the Sudetes, and of young post-glacial sediments containing fragments of Scandinavian crystalline rocks, also enriched with U and Ra, in the area of Mazury-Podlasie monocline. However, the least expected result of the investigations was finding out that, contrary to the hitherto widespread belief, none of the major tectonic units of Poland can be excluded from the list of those containing buildings with mean annual ²²²Rn concentration exceeding 200 Bq/m³. The mean annual concentration of radon for all the buildings were much higher than the mean concentration value (49.1 Bq/m³) of indoor radon in Poland quoted so far. These results cast a completely new light on the necessity to perform measurements of radon concentration in residential buildings in Poland, no more with reference to small areas with outcrops of crystalline rocks (especially the Sudetes, being the Polish fragment of the European Variscan belt), but for all the major tectonic units within Poland.     

A New Approach to Chemical Recycling of Polyamide 6.6 and Synthesis of Polyurethanes with Recovered Intermediates

A new efficient method for the chemical decomposition of polyamide 6.6 by the glycolysis and amino-glycolysis processes was proposed. The glycolysis was conducted using the mass excess of ethylene glycol (EG) as a decomposing agent in the presence of a catalyst. Also, a mixture of EG and triethylenetetramine was used as another decomposing agent in the amino-glycolysis process. The described process of decomposition did not require the use of elevated pressure. The hydroxyl and amine numbers, rheology behavior and the presence of characteristic chemical groups in the obtained glycolysates and aminoglycolysates were determined in order to characterize the reaction products. The decomposition products were defined as non-Newtonian fluids that could be described by suitable mathematical models. The conducted studies showed that the properties of the obtained intermediates depend on the mass excess of the decomposing agent used. The resulting semi-products are suitable for reusing in the synthesis of polyurethanes, which has been confirmed by the exemplary synthesis. In the reaction, 10 and 15 wt% of commercial polyol were replaced with the recovered intermediates.     

Climate and land-use changes affecting river sediment and brown trout in alpine countries—a review

Background, aim, and scope

Catch decline of freshwater fish has been recorded in several countries. Among the possible causes, habitat change is discussed. This article focuses on potentially increased levels of fine sediments going to rivers and their effects on gravel-spawning brown trout. Indications of increased erosion rates are evident from land-use change in agriculture, changes in forest management practices, and from climate change. The latter induces an increase in air and river water temperatures, reduction in permafrost, changes in snow dynamics and an increase in heavy rain events. As a result, an increase in river sediment is likely. Suspended sediment may affect fish health and behaviour directly. Furthermore, sediment loads may clog gravel beds impeding fish such as brown trout from spawning and reducing recruitment rates. To assess the potential impact on fine sediments, knowledge of brown trout reproductive needs and the effects of sediment on brown trout health were evaluated.

Approach

We critically reviewed the literature and included results from ongoing studies to answer the following questions, focusing on recent decades and rivers in alpine countries.

Have climate change and land-use change increased erosion and sediment loads in rivers?

Do we have indications of an increase in riverbed clogging?

Are there indications of direct or indirect effects on brown trout from increased suspended sediment concentrations in rivers or from an increase in riverbed clogging?

Results

Rising air temperatures have led to more intensive precipitation in winter months, earlier snow melt in spring, and rising snow lines and hence to increased erosion. Intensification of land use has supported erosion in lowland and pre-alpine areas in the second half of the twentieth century. In the Alps, however, reforestation of abandoned land at high altitudes might reduce the erosion risk while intensification on the lower, more easily accessible slopes increases erosion risk. Data from laboratory experiments show that suspended sediments affect the health and behaviour of fish when available in high amounts. Point measurements in large rivers indicate no common lethal threat and suspended sediment is rarely measured continuously in small rivers. However, effects on fish can be expected under environmentally relevant conditions. River bed clogging impairs the reproductive performance of gravel-spawning fish.

Discussion

Overall, higher erosion and increased levels of fine sediment going into rivers are expected in future. Additionally, sediment loads in rivers are suspected to have considerably impaired gravel bed structure and brown trout spawning is impeded. Timing of discharge is put forward and is now more likely to affect brown trout spawning than in previous decades.

Conclusions

Reports on riverbed clogging from changes in erosion and fine sediment deposition patterns, caused by climate change and land-use change are rare. This review identifies both a risk of increases in climate erosive forces and fine sediment loads in rivers of alpine countries. Increased river discharge and sediment loads in winter and early spring could be especially harmful for brown trout reproduction and development of young life stages. Recently published studies indicate a decline in trout reproduction from riverbed clogging in many rivers in lowlands and alpine regions. However, the multitude of factors in natural complex ecosystems makes it difficult to address a single causative factor.

Recommendations and perspectives

Further investigations into the consequences of climate change and land-use change on river systems are needed. Small rivers, of high importance for the recruitment of gravel-spawning fish, are often neglected. Studies on river bed clogging are rare and the few existing studies are not comparable. Thus, there is a strong need for the development of methods to assess sediment input and river bed clogging. As well, studies on the effects to fish from suspended sediments and consequences of gravel beds clogging under natural conditions are urgently needed.     

Emissions of isoprene,monoterpene and short-chained carbonyl compounds from Eucalyptus spp. in southern Australia

Eucalypts are among the highest emitters of biogenic volatile organic compounds, yet there is relatively little data available from field studies of this genus. Emissions of isoprene, monoterpenes and the short-chained carbonyls formaldehyde, acetaldehyde and acetone were determined from four species (Eucalyptus camaldulensis, Eucalyptus globulus, Eucalyptus grandis, and Eucalytpus viminalis) in Australia. A smaller comparative study was conducted on E. camaldulensis in south-eastern Australia. Carbonyl emissions, reported here for the first time from eucalypts, were generally comparable with rates reported for other species, with diurnal emissions peaking at about 4, 75 and 34 nmol m^?2 min^?1 for acetone, formaldehyde and acetaldehyde respectively. There was wide variation in diurnal isoprene and monoterpene emissions between species, but under standard conditions, isoprene emissions were much lower than previous reports. Conversely, standard emission rates of monoterpenes were as much as six times greater than previous reports for some species. Emission of each carbonyl was correlated with its ambient concentration across different species, but more weakly related to temperature. Acetaldehyde emission in particular was significantly correlated with transpiration, but not with sap flow or with ethanol concentrations in xylem sap, suggesting fermentation within the leaf and stomatal conductance are primary controlling processes. Differences in acetaldehyde exchange velocities between sites, in addition to transpiration differences, suggest stomata may indeed exert long term emission regulation, in contrast to compounds for which no biological sink exists.     

OPTIMIZATION OF WATER RESOURCES FOR IRRIGATION IN EAST JORDAN1

The paper describes an approach towards optimal allocation of surface and ground water resources to three agricultural areas in the Jordan Valley under conditions of scarce water supply. The optimizing model allocates water from three main rivers, each with reservoir storage, and from two ground water sources to three irrigation regions. Productivity of irrigation water, expressed as the net present value of the regional agricultural output, but allowing for crop water deficits, is first maximized using nonlinear programming. The allocation process then adopts techniques of linear programming to determine the least cost alternative based on the unit cost of water from each resource at each destination, as it varies with time.     

Methods for determination of elemental carbon in ambient air

A few analytical methods of elemental carbon determination are described. The purpose of the work is to choose the best method for determination of its content in dust suspended in air in industrial regions. The reflectance and chromatographic methods were investigated. It was shown that the reflectance methods could be used only when the particle size and form of elemental carbons constant. The chromatographic method, which includes the step of combustion of the sample in oxygen and chromatographic determination of evolved CO₂ is recommended, since it is independent of the form of carbon. Organic carbon is removed from dust samples by extraction with benzene-methanol mixture.     

Weather-driven changes in population density determine wing dimorphism in a bush-cricket species

Long-winged (macropterous) individuals that are capable of flight in predominantly short-winged (flightless) species can considerably affect population dynamics and range expansion. Understanding the triggers that determine macropterism is crucial for understanding whether the dispersal ability of species allows them to shift their distributions through fragmented landscapes or in response to climate change. From 2002 to 2009, we studied population densities and wing dimorphism (macroptery) of Metrioptera roeselii, on 62 plots in central Germany. In the first step, we used a generalized linear mixed-effects model to assess the variables that influence macroptery. Macroptery rates are strongly positively correlated with bush-cricket abundance and not with vegetation structure and habitat moisture. Populations with macropters had significantly higher densities than those without. In the second step, we analysed the relationship between population densities and several mesoclimate/weather parameters. Densities were positively correlated with warm and dry weather conditions during hatching time in April, and previous year weather is less important than present year weather. In the light of the ongoing range expansion of M. roeselii in large parts of Europe, our results support the hypothesis that at high latitudes macropterism and range expansion are indirectly caused by weather-driven changes in population densities.     

Radionuclide and chemical concentrations in mineral waters at Saratoga Springs, New York

A project to characterize the radionuclide and chemical components in natural spring waters in the vicinity of Saratoga Springs, New York (USA) has been completed. As a result of the measured radionuclide and chemical content, eight springs were labeled as mineral waters, whereas three springs contained very low concentrations of these components. The mineral waters were highly enriched in alkaline and alkaline-earth elements, as well as chloride ions. Three isotopes of radium ((224)Ra, (226)Ra, (228)Ra) were detected in the mineral waters and reached concentrations of 1, 20, and 2 Bq/L, respectively. Overall, the (226)Ra isotope constituted about 80% of the total radioactivity measured in the water samples. Dissolved uranium concentrations in the mineral waters were very low (mean approximately 50 mBq/L).     

Thermal Solid State Reactions of Potato Starch with α-Hydroxy Acids

The numerous applications of dextrins resulting from the heating of potato starch with α-amino acids prompted me to check the thermal reactions of starch with hydroxy acids and their lactones, such as citric acid, lactic acid, tartaric acid, and coumarine. The course of reactions was observed by means of Simultaneous TG/DSC Thermal Analyser. The thermal reactions were carried out on convectional and microwave heating. The course of reactions under such conditions was compared and properties of resulting dextrins were recognized. The structure and properties of products were obtained from FTIR spectra, water solubility tests, and pH measurements. It was found, that hydroxy acids and/or products of their thermal transformations reacted with starch and/or resulting dextrins producing esters or crosslinking esterification of dextrins took place. The properties of new dextrins were presented in order to check, in further studies, their application for selective flotation of complex metal ores and their suitability as prebiotics.