A contemporary assessment of polybrominated diphenyl ethers (PBDE) in the ambient air and soil of Azerbaijan

PBDEs were measured in air and soil across Azerbaijan to establish contemporary concentrations at 13 urban and rural sites. Polyurethane foam passive air samplers (PUF-PAS) were deployed for a period of a month with surface soil samples collected at the same sites. Unlike organochlorine pesticides previously surveyed by our group, PBDE concentrations in both contemporary air and soil were low in comparison to recent European and Asian studies. For example, mean ∑₉PBDE concentrations in air and soil were 7.13 ± 1.66 pg m^?3 and 168 ± 57 pg g^?1, respectively. The fully brominated BDE-209 was the most abundant congener observed in soil (174.8 ± 58.5 pg g^?1), comprising ~ 96% of ∑₁₀PBDE. However, the PAS-derived air concentrations for highly brominated congeners must be viewed with caution as there is uncertainty over the uptake rates of particle-bound chemicals using these devices. Some of the highest concentrations in air were observed at sites with the highest wind speeds and at several remote locations in the north of the country and this requires further research. Levels of BDE-47 and 99 (the two most abundant congeners in the widely used penta-formulation) were lower than levels reported elsewhere suggesting limited use/import of the penta-BDE formulation in Azerbaijan.     

Landscape connectivity: A conservation application of graph theory

We use focal-species analysis to apply a graph-theoretic approach to landscape connectivity in the Coastal Plain of North Carolina. In doing so we demonstrate the utility of a mathematical graph as an ecological construct with respect to habitat connectivity. Graph theory is a well established mainstay of information technology and is concerned with highly efficient network flow. It employs fast algorithms and compact data structures that are easily adapted to landscape-level focal species analysis. American mink (Mustela vison) and prothonotary warblers (Protonotaria citrea) share the same habitat but have different dispersal capabilities, and therefore provide interesting comparisons on connections in the landscape. We built graphs using GIS coverages to define habitat patches and determined the functional distance between the patches with least-cost path modeling. Using graph operations concerned with edge and node removal we found that the landscape is fundamentally connected for mink and fundamentally unconnected for prothonotary warblers. The advantage of a graph-theoretic approach over other modeling techniques is that it is a heuristic framework which can be applied with very little data and improved from the initial results. We demonstrate the use of graph theory in a metapopulation context, and suggest that graph theory as applied to conservation biology can provide leverage on applications concerned with landscape connectivity.     

Trampling impact on vegetation of embryonic and stabilised sand dunes in Montenegro

Trampling is one of the human activities that are harmful for plant species and communities of sand dune ecosystems. The aim of this study was to compare the vegetation of embryonic and shifting Ammophila sand dunes with and without fencing to limit trampling. Fenced sand dunes appeared to be richer in species but differences were more prominent in embryonic sand dunes. Some species (Cakile maritima, Pancratium maritimum) were missing on trampled embryonic dunes. The positive impact of trampling exclusion on embryonic sand dunes was indicated by a lowered slope in a Whittaker graph as well as by rarefaction curves that showed higher species richness on the lower slope. Changes in the vegetation of more stabilised shifting Ammophila sand dunes due to trampling are not evident, although species composition is also impoverished. Fencing of parts of sand dunes proved to be an effective measure for vegetation conservation. In addition to physical exclusion of visitors, fences can also have symbolic value for raising public awareness.     

Trends and events through seven centuries: the history of a wetland landscape in the Czech Republic

Environmental change can be viewed as the combined result of long-term processes and singular events. While long-term trends appear to be readily available for observation (in the form of temporal comparisons or space-for-time substitution), it is more difficult to gain information on singular events in the past, although these can be equally significant in shaping ecosystems. We examined the past 700 years in the history of a lowland wetland landscape in the Czech Republic with the help of palaeoecological, ecological, landscape archaeological, and archival data. Macrofossil and pollen data were compared to known drainage works in the area and historical climatological data. Trends and events in habitat conditions were assessed using species indicator values. Results showed that ecological succession was the general process in the study area, detected as a trend towards eutrophication, desiccation, and vegetation closure. Short-term events influenced development at the sites mainly from the second half of the nineteenth century. This is consistent with drainage history, although bias related to sample frequency cannot be excluded. On the whole, long-term trends and discrete events were complementary on different scales. We conclude that humans facilitated and accelerated background processes, which can be most likely associated with the succession of open wetlands towards terrestrial ecosystems.     

Downstream Dissipation of Storm Flow Heat Pulses: A Case Study and its Landscape‐Level Implications

Storms in urban areas route heat and other pollutants from impervious surfaces, via drainage networks, into streams with well‐described negative consequences on physical structure and biological integrity. We used heat pulses associated with urban storms as a tracer for pavement‐derived stormwater inputs, providing a conservative estimate of the frequency with which these pollutants are transported into and through protected stream reaches. Our study was conducted within a 1.5‐km reach in Durham, North Carolina, whose headwaters begin in suburban stormwater pipes before flowing through 1 km of protected, 100‐year‐old forest. We recorded heat‐pulse magnitudes and distances travelled downstream, analyzing how they varied with storm and antecedent flow conditions. We found heat pulses >1°C traveled more than 1 km downstream of urban inputs in 11 storms over one year. This best‐case management scenario of a reach within a protected forest shows that urban impacts can travel far downstream of inputs. Air temperature and flow intensity controlled heat‐pulse magnitude, while heat‐pulse size, mean flow, and total precipitation controlled dissipation distance. As temperatures and sudden storms intensify with climate change, heat‐pulse magnitude and dissipation distance will likely increase. Streams in urbanized landscapes, such as Durham municipality, where 98.9% of streams are within 1 downstream km of stormwater outfalls, will be increasingly impacted by urban stormwaters.     

Replacing monocultures with mixed-species stands: Ecosystem service implications of two production forest alternatives in Sweden

Whereas there is evidence that mixed-species approaches to production forestry in general can provide positive outcomes relative to monocultures, it is less clear to what extent multiple benefits can be derived from specific mixed-species alternatives. To provide such insights requires evaluations of an encompassing suite of ecosystem services, biodiversity, and forest management considerations provided by specific mixtures and monocultures within a region. Here, we conduct such an assessment in Sweden by contrasting even-aged Norway spruce (Picea abies)-dominated stands, with mixed-species stands of spruce and birch (Betula pendula or B. pubescens), or spruce and Scots pine (Pinus sylvestris). By synthesizing the available evidence, we identify positive outcomes from mixtures including increased biodiversity, water quality, esthetic and recreational values, as well as reduced stand vulnerability to pest and pathogen damage. However, some uncertainties and risks were projected to increase, highlighting the importance of conducting comprehensive interdisciplinary evaluations when assessing the pros and cons of mixtures.     

Spatially valid data of atmospheric deposition of heavy metals and nitrogen derived by moss surveys for pollution risk assessments of ecosystems

For analysing element input into ecosystems and associated risks due to atmospheric deposition, element concentrations in moss provide complementary and time-integrated data at high spatial resolution every 5 years since 1990. The paper reviews (1) minimum sample sizes needed for reliable, statistical estimation of mean values at four different spatial scales (European and national level as well as landscape-specific level covering Europe and single countries); (2) trends of heavy metal (HM) and nitrogen (N) concentrations in moss in Europe (1990–2010); (3) correlations between concentrations of HM in moss and soil specimens collected across Norway (1990–2010); and (4) canopy drip-induced site-specific variation of N concentration in moss sampled in seven European countries (1990–2013). While the minimum sample sizes on the European and national level were achieved without exception, for some ecological land classes and elements, the coverage with sampling sites should be improved. The decline in emission and subsequent atmospheric deposition of HM across Europe has resulted in decreasing HM concentrations in moss between 1990 and 2010. In contrast, hardly any changes were observed for N in moss between 2005, when N was included into the survey for the first time, and 2010. In Norway, both, the moss and the soil survey data sets, were correlated, indicating a decrease of HM concentrations in moss and soil. At the site level, the average N deposition inside of forests was almost three times higher than the average N deposition outside of forests.     

Simultaneous determination of pesticides,mycotoxins, tropane alkaloids,growth regulators,and pyrrolizidine alkaloids in oats and whole wheat grains after online clean-up via two-dimensional liquid chromatography tandem mass spectrometry

In this study, a two-dimensional liquid chromatography tandem mass spectrometry method was developed and validated for the determination of pesticide residues and contaminants in whole wheat grains and oats. The samples were extracted with a mixture of acetonitrile and water and were injected into the two-dimensional LC-MS/MS system without any further clean-up or sample preparation. Samples were analyzed with four different matrix matched calibrations. Matrix effects were evaluated by comparing analyte signals in the respective matrix matched standard with the neat solvent standards. The final method was validated according to the current Eurachem validation guide and SANTE document. The number of successfully validated analytes throughout all three validation levels in oats and wheat, respectively, were as follows: 330 and 316 out of 370 pesticides, 6 and 13 out of 18 pyrrolizidine alkaloids and 7 out of 9 regulated mycotoxins. Moreover, both plant growth regulators mepiquat and chlormequat as well as the tropane alkaloids atropine and scopolamine met the validation criteria. The majority of pesticides showed limits of detection below 1?µg kg^?1, pyrrolizidine alkaloids below 0.7?µg kg^?1, tropane alkaloids below 0.2?µg kg^?1, growth regulators below 0.7?µg kg^?1 and mycotoxins below 8?µg kg^?1 in both matrices.     

Concentration of Organochlorine Pollutants in Surface Waters of the Central European Biosphere Reserve Krivoklatsko (8 pp)

Background, Aim and Scope The article is focused on dioxin, furan, PCB and organochlorine pesticide monitoring in the surface waters of the Central European, protected natural reserve Krivoklatsko, under the UNESCO programme Man and Biosphere. Persistent compounds are presently transported via different means throughout the entire world. This contamination varies significantly between sites. This raises the question of what constitutes the naturally occurring background levels of POPs in natural, unpolluted areas, but which are close to industrialised regions. Information of real background POP contamination can be of high value for risk assessment management of those sites evidently polluted and for the defining of de-contamination limits. Preserved areas should not be seen as isolated regions in which the impacts of human activities and natural factors are either unexpected or overlooked. Every ambient region, even those protected by a law or other means, are still closely connected to neighbouring human developed and impacted areas, and are therefore subject to this anthropogenic contamination. These areas adjacent to natural reserves are sources of diverse substances, via entry of air, water, soil and/or biota. After an extended period of industrial activities, organochlorine pollutants, even those emitted in trace concentrations have reached detectable levels. For future research and for the assessment of environmental changes, present levels of contamination would be of high importance. This work publishes data of the contamination with organochlorine pollutants of this natural region, where biodiversity and ecological functions are of the highest order. Materials and Methods: Semipermeable membrane devices (SPMDs) were utilised as the sampling system. SPMDs were deployed in two small creeks and one water reservoir selected in the central part of the Krivoklatsko Natural Reserve, where it could be expected that any possible contamination by POPs would be lowest. The exposed SPMDs were analysed both for chemical contents of POPs and for toxicity properties. The chemical analyses of dibenzo-dioxins, dibenzo-furans, PCBs and OCPs were analysed by GC/MS/MS on GCQ or PolarisQ (Thermoquest). Toxicity bioassays were performed on the alga Desmodesmus subspicatus, bacteria Vibrio fischeri and crustacean Daphnia magna. All toxicity data were expressed as the effective volume Vtox. Vtox is a toxicity parameter, the determination of which is independent of SPMD deployment time and pre-treatment dilution (unlike, for example, the EC50 of the SPMD extract). Results: The following chemical parameters were monitored: 1) tetra, penta, hexa and hepta dibenzo-p-dioxins and furans; 2) all those detectable from tri- through deca-polychloriated biphenyls (PCBs) and 3) a group of organochlorine pesticides: hexachlorobenzene and isomers of hexachlorocyclohexane, DDE, DDD and DDT. The concentrations of dioxins and furans on the assessed sites varied from under detection levels up to 7 pg.l-1; PCBs were detected in a sum concentration up to 2.8 ng.l-1; and organochlorine pesticides up to 346 pg.l-1. The responses of bioassays used were very low, with the values obtained for Vtox being under 0.03 l/d. Discussion: Toxicity testing showed no toxicity responses, demonstrating that the system used is in coherence with the ecological status of the assessed sites. Values of Vtox were under the critical value – showing no toxicity. The PCA of chemical analysis data and toxicity responses resulted in no correlations between these two groups of parameters. This demonstrated that the present level of contamination has had no direct adverse effects on the biota. Conclusions: The concentration values of six EPA-listed, toxic dioxins and sums of tetra-hepta dioxins; nine EPA toxic dibenzofurans and the sums of tetra-hepta bibenzofurans are presented together with all tri-deka PCBs and organochlorine pesticides (alfa-, beta-, gama-, delta-HCH, HCB, opDDE, ppDDE, opDDD, ppDDD, opDDT, ppDDT). These values represent possible current regional natural background values of these substances monitored within the Central European region, with no recorded adverse effects on the freshwater ecosystem (up until the present time). Recommendations and Perspectives: Assessment of dioxins, furans and other organochlorine compounds within natural reserves can be important for the monitoring of human-induced impacts on preserved areas. No systematic monitoring of these substances in areas not directly affected by industry has generally been realised. There is a paucity of data of the presence of any of these substances within natural regions. Further monitoring of contamination of both soil and biota by dioxins and furans in preserve regions is needed and can be used for future monitoring of man-made activities and/or accidents. Semipermeable membrane devices proved to be a very good sampling system for the monitoring of trace concentrations of ambient organochlorine compounds. Toxicity evaluation using the Vtox concept demonstrated that those localities assessed expressed no toxicity.