Optimization of selective pressurized liquid extraction for extraction and in-cell clean-up of PCDD/Fs in soils and sediments

This paper describes the development of methods for selective extraction of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from soils and sediments, using pressurized liquid extraction with in-cell clean-up (SPLE). Two binary solvent mixtures, viz. dichloromethane/n-heptane (DCM/Hp), and diethylether/n-heptane (DEE/Hp), were evaluated. The SPLE extraction conditions were optimized using central composite face (CCF) design. Three factors were investigated: extraction temperature (60–160 °C), number of extraction cycles (1–3) and time per cycle (2–18 min). The results showed that DCM/Hp (1/1, v/v) and DEE/Hp (1/2, v/v) were the best extraction solvent compositions and that the extraction temperature was a critical factor that needed careful optimization to achieve high extraction efficiency without co-extraction of sulfuric acid. Under the optimal conditions, the SPLE methods provided results with good accuracy and precision. For the sandy soil certified reference material (CRM-529) the quantification results ended up in the range 82–110% as compared to the concentrations obtained by a reference method based on Soxhlet extraction and external column clean-up. Furthermore, for a clay soil (CRM-530) and a sediment reference material (WMS-01), the accuracy (trueness) of the TEQ values were +11% (DCM/Hp) and +8% (DEE/Hp) for CRM-530, +8% and ?7% for WMS-01, respectively. The individual congener concentrations also agreed well with the certified values. These findings show that SPLE is a promising method for combined extraction and clean-up of PCDD/Fs in soil/sediment samples.     

Determinations of PCB within a project to develop cleanup methods for PCB-containing elastic sealant used in outdoor joints between concrete blocks in buildings

Determinations of PCB were carried out as part of a project aimed at developing cleanup methods for PCB-containing elastic sealant used in outdoor joints between concrete blocks. The goals of the project were to develop methods, which minimise the spread of PCB to the outdoor environment and to indoor air, and which keep the PCB levels as low as reasonably possible in the workplace environment whilst removing the elastic sealant. The following PCB determinations were carried out: (1) concentration in the elastic sealant; (2) concentration in the concrete close to the sealant; (3) concentration in soil; (4) concentration in the indoor air; and (5) concentration in the air in the workplace environment. The cleanup process consisted of a number of different steps: (1) cutting the elastic sealant with an oscillating knife; (2) grinding the concrete with a mechanical machine; (3) sawing the concrete with a mechanical saw and (4) cutting the concrete with a mechanical chisel. In all these different steps a high capacity vacuum cleaner connected to the machines was used. The elastic sealant contained 4.7 to 8.1% total PCB of a technical product with a composition most similar to Clophene A40. The concrete close to the sealant (first 2 mm) contained 0.12 and 1.7% total PCB at two different places. The pattern of the PCB in the concrete resembled that of the sealant. PCB concentrations in the soil from the ground close to the building were 0.1 and 0.3 ppm at two different places before the remedial action. The source of the PCB in the soil is most likely the sealant as the PCB pattern is similar for the two materials. The PCB levels in the workplace air at the beginning of the project, when the techniques were not fully developed, were generally above the occupational exposure limit of 10 micrograms m-3 (up to 120 micrograms m-3). Later when the techniques were optimised to better take care of dust and gases produced during the cutting and grinding etc., the levels were below or close to 10 micrograms m-3. The pattern of the PCB in the workplace air was different from that of the sealant and contained higher levels of lighter components. The PCB concentrations in the indoor air were measured before and during the remedial process. The levels were around 600 ng m-3 and there was no significant increase during the removal of the sealant. The PCB level after the remedial action will be measured later. The pattern of the PCB in the indoor air was different from that of the sealant as well as from that of the workplace air. Higher levels of the lighter PCB were present indoors compared to the composition in both workplace air and in sealant. Extracts of PCB were analysed by GC-MS with a SIM method (selected ion monitoring). Standard procedures were used for extraction of solid materials. For the air samples an OVS tube was used with XAD-2 as adsorbent. The filter and adsorbent were extracted with toluene. This work shows that it is important to perform remedial action of PCB-containing elastic sealant as: (1) there is a spread of PCB to the indoor air giving high enough concentrations to make this the main PCB load on humans living in the apartments studied in this project; (2) large amounts are spread to the soil from these sealants; and (3) many of the PCB-containing elastic sealants used need to be changed from a functional perspective.     

CLFUG: A GIS‐scaleable model of pesticide fate in the soil–groundwater system based on clearance and fugacity paradigms

A model of pesticide transport through the soil profile based on clearance and fugacity paradigms is presented, and an example of its application in a GIS environment is shown. A validation of the model at the field plot scale is presented using data obtained at a crop in a semiarid irrigated agricultural basin which was treated with Lindane. The adequacy at the regional scale is tested by inspection of the model predictions and the measured concentrations of the pesticide obtained from a regional phreatimetric net. The clearance concept is used to obtain estimates of the volumes of some environmental phases. These are further used to solve the equations of thermodynamic equilibrium at equal fugacity and obtain concentration estimates. The model closely reproduces the observed percolation trends, and is consistent with the regional pattern of Lindane distribution in groundwater. An application of the model as unitary module for the simulation of non‐point pesticide sources in a raster GIS frame is shown. Its performance (run time, data needed, etc.) is comparable to that of other existing algorithms, and presents some advantages to planners and evaluators of environmental quality in that it incorporates an explicit 2‐D approach and allows the identification of polluted areas downslope with respect to those directly treated with the pesticides. Further, it can be implemented in a variety of GIS and spatial data processors.     

Half a century of changing mercury levels in Swedish freshwater fish

The variability of mercury (Hg) levels in Swedish freshwater fish during almost 50 years was assessed based on a compilation of 44 927 observations from 2881 waters. To obtain comparable values, individual Hg concentrations of fish from any species and of any size were normalized to correspond to a standard 1-kg pike [median: 0.69 mg kg^?1 wet weight (ww), mean ± SD: 0.84 ± 0.67 mg kg^?1 ww]. The EU Environmental Quality Standard of 0.02 mg kg^?1 was exceeded in all waters, while the guideline set by FAO/WHO for Hg levels in fish used for human consumption (0.5–1.0 mg kg^?1) was exceeded in 52.5 % of Swedish waters after 2000. Different trend analysis approaches indicated an overall long-term decline of at least 20 % during 1965–2012 but trends did not follow any consistent regional pattern. During the latest decade (2003–2012), however, a spatial gradient has emerged with decreasing trends predominating in southwestern Sweden.     

Do associated zooxanthellae and the nature of the substratum affect survival,attachment and growth of Cliona viridis (Porifera: Hadromerida)? An experimental approach

Massive specimens of Cliona viridis, collected off the coast of Blanes (North-Western Mediterranean Sea) in January 1987, were exposed to different light (natural day-night irradiance/constant darkness) and substrata (calcareous/siliceous) conditions to assess their influence on growth, survival and attachment rates. Sponges cultured under natural irradiance displayed higher growth rates with increasing temperature; those cultured in the dark did not respond to increased temperature, but adapted faster to laboratory conditions. Differences in growth rates between these two culture conditions are ascribed to the presence of a healthy symbiotical zooxanthellae population on individuals cultured under conditions of natural irradiance. Attachment rates of the cut sides of the sponges which were in direct contact with the substratum, also increased with increasing temperature, whilst sponge survival was not significantly dependent on temperature. The chemical nature of the substratum clearly affected survival rates, which were higher on calcified than on siliceous substrata.     

Bird orientation: Single homing pigeons compared with small flocks

Summary The hypothesis that bird flocks orient more accurately than single individuals was tested on homing pigeons. Birds were released both singly and in flocks of three to six. Vanishing bearings were recorded and it was found that flocks were less scattered around the mean direction than singly released birds. Homing times were found to be shorter for flocks as compared to singles. This suggests that the average homing pigeon can gain in directional accuracy and save energy by joining other pigeons heading for the same goal.     

Swedish perspectives on the future of raw materials

The author describes a futures study which looked at the long term supply of raw materials and resources for Sweden. The study involves the construction of a number of possible scenarios of Swedish and world development and an examination of their implications for resource supply. The conclusion is that there are unlikely to be any physical limits to growth over the next 25 years or so but that there may well be political obstacles. In any event, ideas of development are largely conditioned by historical and social circumstances and new paradigms may well produce new models of development.     

Territory ownership and familiarity status affect how much male root voles (Microtus oeconomus) invest in territory defence

Neighbour–stranger discrimination occurs when individuals respond with more aggression to strangers than to territorial neighbours—a phenomenon termed the “dear enemy phenomenon” (DEP). We investigated the DEP with male and female root voles (Microtus oeconomus Pallas 1776) using field dyadic arena tests conducted in enclosures where we could test for the effects of familiarity (familiar versus stranger), ownership (resident versus intruder status) and resource-holding potential (body mass) on territorial behaviours. The results showed that males put more effort into territorial defence than females, and males could discriminate between neighbours and strangers. In males, aggressiveness was influenced by a significant two-way interaction between treatment and ownership. Male residents were more aggressive towards stranger intruders than towards neighbour intruders, while male intruders were less aggressive towards stranger residents than towards neighbour residents. In females, neither treatment nor ownership status had a significant effect on aggressiveness. Familiar males performed more social behaviours but less non-social behaviours than stranger males. Furthermore, there was a clear dominance hierarchy between residents and intruders in stranger dyads, with the male territory holders dominating the intruder in pairwise interactions. To our knowledge, these results demonstrate for the first time DEP in a small mammal with a known pedigree and present the first evidence for “prior resident advantage” in voles. We argue that both ownership status and familiarity status affect how much an individual invests in territory defence. The benefits of neighbour–stranger discrimination for male root voles and the absence of neighbour–stranger discrimination in female root voles are discussed.     

Cultivated land – a scarce commodity in a densely populated rural area in South Wollo,Ethiopia

Cultivated and settlement areas were studied in a small area (14 km2) in South Wollo, Ethiopia, by aerial photos, satellite images, field observations and interviews. Areas for cultivation/rural settlement decreased a few per cent between 1958 and 2013. Cultivated land per household slowly decreased in 1958–2003 but in 2003–2013 the annual decrease was 3–4 times higher. New farm buildings are often built on cultivated land, and abandoned buildings areas return to cultivation. Rainwater harvesting ponds have increased the areas with perennial crops that are important as a source of income. Tin roofed buildings are signs of improved livelihood. Very small farm size and rain-dependent agriculture combined with climate variability make food security vulnerable. Land-use inventories including remote sensing and local knowledge would be a valuable approach to assess livelihood needs. Further, it should involve decision makers at different levels, but local agricultural extension officers may play a central role.     

Territory and group sizes in Eurasian beavers (Castor fiber): echoes of settlement and reproduction?

According to current theories of territoriality, an animal is expected to defend the smallest area that can provide resources for maximisation of reproduction, known as the economically defendable area. In group territorial species however, the strategies behind resource defence are likely to be more complex with corporate territoriality, cooperative breeding, delayed dispersal and intra-group competition all potentially playing a role. Here we examined group territoriality in a social herbivorous rodent, the Eurasian beaver Castor fiber. Beavers in our study do not inhabit economically defendable territories. Instead the sequence of arrival of pairs into unoccupied areas seems to play a more important role in determining the size of the territory, whereas group size is determined by past reproductive success. We argue that the settlement pattern and reproductive history have a lasting impact in the territorial system of beavers due to a combination of the low adult mortality, high dispersal costs, and avoidance of resource depletion.R.D. Campbell and F. Rosell contributed equally to this work