Organic carbon causes interference with nitrate and nitrite measurements by UV/Vis spectrometers: the importance of local calibration

Compared with sporadic conventional water sampling, continuous water-quality monitoring with optical sensors has improved our understanding of freshwater dynamics. The basic principle in photometric measurements is the incident light at a given wavelength that is either reflected, scattered, or transmitted in the body of water. Here, we discuss the transmittance measurements. The amount of transmittance is inversely proportional to the concentration of the substance measured. However, the transmittance is subject to interference, because it can be affected by factors other than the substance targeted in the water. In this study, interference with the UV/Vis sensor nitrate plus nitrite measurements caused by organic carbon was evaluated. Total or dissolved organic carbon as well as nitrate plus nitrite concentrations were measured in various boreal waters with two UV/Vis sensors (5-mm and 35-mm pathlengths), using conventional laboratory analysis results as references. Organic carbon increased the sensor nitrate plus nitrite results, not only in waters with high organic carbon concentrations, but also at the lower concentrations (< 10 mg C L^?1) typical of boreal stream, river, and lake waters. Our results demonstrated that local calibration with multiple linear regression, including both nitrate plus nitrite and dissolved organic carbon, can correct the error caused by organic carbon. However, high-frequency optical sensors continue to be excellent tools for environmental monitoring when they are properly calibrated for the local water matrix.     

Spatial variation in soil carbon in the organic layer of managed boreal forest soil—implications for sampling design

We studied within-site spatial variation of the carbon stock in the organic layer of boreal forest soil. A total of 1,006 soil samples were taken in ten forest stands (five Scots pine stands and five Norway spruce stands). Our results indicate that the spatial autocorrelation disappears at a distance of 75-225 cm. This spatial autocorrelation should be taken into account in the sampling design by locating the sampling points at adequate intervals. With a sample size of over 20-30 samples per site, additional soil samples do not notably improve the precision of the site mean estimate. An adequate sample size is dependent on the purpose of sampling and on the site-specific soil variation. Our results on the dependence between sample size and precision of the mean estimates can be applied in designing efficient soil monitoring in boreal coniferous forests.     

Changes in the heavy metal and nutrient contents of dried feather mosses during long-term storage

This study measured heavy metal and nutrient concentrations of two feather mosses during the periods of dry storage. Samples (Hylocomium splendens, Pleurozium schreberi) were collected in the nationwide moss surveys carried out on the permanent sample plots of the 8th Finnish National Forest Inventory in 1985–86, 1990, 1995 and 2000. A small amount of each moss sample was analyzed soon after collection, and the remainder was dried and stored at the Paljakka environmental specimen bank (ESB). The 108 stored samples from 27 plots were reanalyzed in 2008. Concentrations of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) and nutrients (Ca, K, Mg, P) were determined and compared for each survey year. Overall, Fe, Pb and Cr concentrations decreased, and Cu concentrations increased significantly during storage. The greatest decrease was observed in samples from plots where their initial concentrations were the highest. Changes in the concentrations of Cd, Ni and Zn were less pronounced. The loss of heavy metals is likely due to drying when cell membranes rupture and some of the surface material is lost. K, P and, to some extent, Mg concentrations increased during storage, whereas Ca did not change significantly. Nutrient increase is probably due to their movement from older to younger growths during the initial phase of drying. Ca is mostly bound to cell walls and is not easily released. Results emphasize the importance of establishing the intended use of a stored moss prior to sampling, in order to select and optimize an appropriate storage technique.     

Urban mining: hibernating copper stocks in local power grids

Large technical systems serving the everyday needs of people, such as water supply systems, power grids or communication networks, are rich in accumulated metals. Over time, parts of these systems have been taken out of use without the system infrastructure being removed from its original location. Such metal stocks in hibernation thus constitute potential resource reservoirs accessible for recovery. In this paper, obsolete stocks of copper situated in the local power grids of two Swedish cities are quantified. Emphasis is also on economic conditions for extracting such “hibernating” cables. The results show that on a per customer basis, the two power grids contain similar amounts of copper, i.e. 0.04–0.05 tonnes per subscriber. However, the share of the copper stock that is in hibernation differs between the grids. In the larger grid of Gothenburg, almost 20% of the copper accumulated in the grid is no longer in use, while the obsolete share does not exceed 5% in the city of Linköping. For managers of local power grids, recovery of hibernating cables could be beneficial if integrated with other maintenance work on the grid. At the present price of copper, however, separate recovery of obsolete cables is not economically justified.     

Treatment of hydrocarbon contamination under flow through conditions by using magnetite catalyzed chemical oxidation

Soil pollution by hydrocarbons (aromatic and aliphatic hydrocarbons) is a major environmental issue. Various treatments have been used to remove them from contaminated soils. In our previous studies, the ability of magnetite has been successfully explored to catalyze chemical oxidation for hydrocarbon remediation in batch slurry system. In the present laboratory study, column experiments were performed to evaluate the efficiency of magnetite catalyzed Fenton-like (FL) and activated persulfate (AP) oxidation for hydrocarbon degradation. Flow-through column experiments are intended to provide a better representation of field conditions. Organic extracts isolated from three different soils (an oil-contaminated soil from petrochemical industrial site and two soils polluted by polycyclic aromatic hydrocarbon (PAH) originating from coking plant sites) were spiked on sand. After solvent evaporation, spiked sand was packed in column and was subjected to oxidation using magnetite as catalyst. Oxidant solution was injected at a flow rate of 0.1 mL min^?1 under water-saturated conditions. Organic analyses were performed by GC–mass spectrometry, GC–flame ionization detector, and micro-Fourier transform infrared spectroscopy. Significant abatement of both types of hydrocarbons (60–70 %) was achieved after chemical oxidation (FL and AP) of organic extracts. No significant by-products were formed during oxidation experiment, underscoring the complete degradation of hydrocarbons. No selective degradation was observed for FL with almost similar efficiency towards all hydrocarbons. However, AP showed less reactivity towards higher molecular weight PAHs and aromatic oxygenated compounds. Results of this study demonstrated that magnetite-catalyzed chemical oxidation can effectively degrade both aromatic and aliphatic hydrocarbons (enhanced available contaminants) under flow-through conditions.     

Fine Particle (PM25) Measurement Methodology,Quality Assurance Procedures,and Pilot Results of the EXPOLIS Study

ABSTRACT

EXPOLIS is a European multicenter (Athens, Basel, Grenoble, Helsinki, Milan, and Prague) air pollution exposure study. It is the first international, population-based, large-scale study, where personal exposures to PM_{2 5} aerosol particles (together with volatile organic compounds and carbon monoxide) are being monitored. EXPOLIS is performed in six different centers across Europe, the sampled aerosol concentrations vary greatly, and the mi-croenvironmental samples are not collected with the same equipment as the personal samples. Therefore careful equipment selection, methods development and testing, and thorough quality assurance and quality control (QA & QC) procedures are essential for producing reliable and comparable PM_2.5 data. This paper introduces the equipment, the laboratory test results, the pilot results, the standard operating procedures, and the QA & QC procedures of EXPOLIS. Test results show good comparability and repeatability between personal and microenvironmen-tal monitors for PM2.5 at different concentration levels measured across Europe in EXPOLIS centers.     

A Field Intercomparison and Fundamental Characterization of Various Dust Samplers with a Reference Sampler

The European Economic Community Council Directive 80/779/EEC¹ describes air quality limit values and guide values for sulfur dioxide and suspended particulates. However, article 10, paragraph 1 does not define well enough the reference method required, amongst others, for the gravimetric measurement of suspended particulates. It is explicity stated in article 10, paragraph 5 of the directive, that “the commission shall, in selected locations in the member states and in cooperation with the latter, carry out studies on the sampling…of suspended particulates. These studies shall be designed in particular to promote the harmonization of methods of sampling and analysis of these pollutants.” Therefore, in a joint research program the Umweltbundesamt (grant #104 02263), the commission of European Communities (grant #84-B-6642-11-017-11-N) and the U.S. EPA (grant #2-43211-3580) funded the development of a reference dust sampler by the Fraunhofer-lnstitute of Toxicology and Aerosol Research (FhITA, in Hannover, Federal Republic of Germany) in order: ? to study the particle size distribution of ambient air aerosol at a number of selected sites;

? to compare the results obtained with the reference dust sampler with those of particle samplers operated in Europe and the United States;

? to verify the applicability of wind tunnel results to sampling behaviour in the free atmosphere.

     

Sperm competition affects sex allocation but not sperm morphology in a flatworm

Sperm competition has been shown to be an important evolutionary agent affecting the behaviour, physiology, and morphology of both males and females. One morphological trait that is particularly likely to be affected by sperm competition is sperm size because it is thought to influence the competitiveness of sperm by determining sperm longevity, motility, and/or their ability to displace competing sperm. Most comparative studies across taxa have found a positive relationship between the level of sperm competition and sperm length, but very few studies have tested for a phenotypically plastic adjustment of sperm morphology in response to sperm competition. In this study, we experimentally tested for an effect of sperm competition on phenotypic plasticity in sperm morphology in an obligately outcrossing simultaneous hermaphrodite, the free-living flatworm Macrostomum lignano, by either raising worms in monogamous pairs (no sperm competition) or in promiscuous groups (intense sperm competition). Worms in groups produced larger testes and smaller ovaries as predicted by sex allocation theory and as previously documented in this species. However, we found no evidence for an effect of group size on sperm morphology, measured as total sperm length, sperm body length, and the length of two different sperm appendages. We conclude that M. lignano may either be incapable of adjusting the sperm morphology in a phenotypically plastic way and/or that there might be no benefit of phenotypic plasticity in sperm traits in this species.     

Distribution,fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, ¹⁴C- and ¹³C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied ¹⁴C was mineralized. The bioavailable, water extractable portion was low (9 % of applied ¹⁴C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied ¹⁴C was incorporated into organo-clay complexes as NER, whereas 9 % of applied ¹⁴C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.