The pH-dependent adsorption of tributyltin to charcoals and soot

Widespread use of tributyltin (TBT) poses a serious environmental problem. Adsorption by black carbon (BC) may strongly affect its behavior. The adsorption of TBT to well characterized soot and two charcoals with specific surface area in the range of 62-111 m² g⁻¹ have been investigated with main focus on pH effects. The charcoals but not soot possess acidic functional groups. TBT adsorption reaches maximum at pH 6-7 for charcoals, and at pH > 6 for soot. Soot has between 1.5 and 15 times higher adsorption density (0.09-1.77 μmol m⁻²) than charcoals, but charcoals show up to 17 times higher sorption affinities than soot. TBT adsorption is successfully described by a new pH-dependent dual Langmuir model considering electrostatic and hydrophobic adsorption, and pH effects on TBT speciation and BC surface charge. It is inferred that strong sorption of the TBTOH species to BC may affect TBT toxicity.     

The impact of swidden decline on livelihoods and ecosystem services in Southeast Asia: A review of the evidence from 1990 to 2015

Global economic change and policy interventions are driving transitions from long-fallow swidden (LFS) systems to alternative land uses in Southeast Asia’s uplands. This study presents a systematic review of how these transitions impact upon livelihoods and ecosystem services in the region. Over 17 000 studies published between 1950 and 2015 were narrowed, based on relevance and quality, to 93 studies for further analysis. Our analysis of land-use transitions from swidden to intensified cropping systems showed several outcomes: more households had increased overall income, but these benefits came at significant cost such as reductions of customary practice, socio-economic wellbeing, livelihood options, and staple yields. Examining the effects of transitions on soil properties revealed negative impacts on soil organic carbon, cation-exchange capacity, and aboveground carbon. Taken together, the proximate and underlying drivers of the transitions from LFS to alternative land uses, especially intensified perennial and annual cash cropping, led to significant declines in pre-existing livelihood security and the ecosystem services supporting this security. Our results suggest that policies imposing land-use transitions on upland farmers so as to improve livelihoods and environments have been misguided; in the context of varied land uses, swidden agriculture can support livelihoods and ecosystem services that will help buffer the impacts of climate change in Southeast Asia.     

Community assembly in experimental grasslands: suitable environment or timely arrival?

It is hard to defend the view that biotic communities represent a simple and predictable response to the abiotic environment. Biota and the abiotic environment interact, and the environment of an individual certainly includes its neighbors and visitors in the community. The complexity of community assembly calls forth a quest for general principles, yet current results and theories on assembly rules differ widely. Using a grassland microcosm as a model system, we manipulated fertility, disturbance by defoliation, soil/microclimate, and arrival order of species belonging to two groups differing in functional attributes. We analyzed the outcome of community assembly dynamics in terms of species richness, invasibility, and species composition. The analyses revealed strong environmental control over species richness and invasibility. Species composition was mainly determined by the arrival order of species, indicating that historical contingency may change the outcome of community assembly. The probability for multiple equilibria appeared to increase with productivity and environmental stability. The importance of arrival order offers an explanation of the difficulties in predicting local occurrences of species in the field. In our experiment, variation in fertility and disturbance was controlling colonization with predictable effects on emergent community properties such as species richness. The key mechanism is suggested to be asymmetric competition, and our results show that this mechanism is relatively insensitive to the species through which it works. While our analyses indicate a positive and significant correlation between richness and invasibility, the significance disappears after accounting for the effect of the environment. The importance of arrival order (historical contingency) and environmental control supports the assumption of the unified neutral theory that different species within a trophic level can be considered functionally equivalent when it comes to community assembly. However, our results indicate that variation in asymmetric competition is the key factor determining the richness of the resulting communities, and this is far from neutral.     

Degradation and mobility of linear alkylbenzene sulfonate and nonylphenol in sludge-amended soil

Degradation and mobility of the surfactants linear alkylbenzene sulfonate (LAS) and nonylphenol (NP) were investigated in a lysimeter study using a sandy loam soil and 45-cm soil columns. Anaerobically digested sewage sludge was incorporated in the top-15-cm soil layer to an initial content of 38 mg LAS and 0.56 mg NP kg(-1) dry wt., respectively. Spring barley (Hordeum vulgare L.) was sown onto the columns. The lysimeters were placed outdoors and therefore received natural precipitation, but were also irrigated to a total amount of water equivalent to 700 mm of precipitation. Leachate and soil samples from three soil layers were collected continuously during a growth period of 110 d. Leachate samples and soil extracts were concentrated by solid-phase extraction (SPE) and analyzed using high performance liquid chromatography (HPLC) with fluorescence detection. The concentrations in the top-15-cm soil layer declined to 25 and 45% of the initial contents for LAS and NP, respectively, within the first 10 d of the study. At the end of the study, less than 1% LAS was left, while the NP content was below the detection limit. Assuming first-order degradation kinetics, half-lives of 20 and 37 d were estimated for LAS and NP, respectively. The surfactants were not measured in leachate samples in concentrations above the analytical detection limits of 4.0 and 0.5 microg L(-1) for LAS and NP, respectively. In addition, neither LAS nor NP were measured in concentrations above the detection limits of 150 and 50 microg kg(-1) dry wt., respectively, in soil layers below the 15 cm of sludge incorporation, indicating negligible downward transport of the surfactants in the lysimeters.     

Sorption of lambda-cyhalothrin,cypermethrin, deltamethrin and fenvalerate to quartz,corundum, kaolinite and montmorillonite

Sorption to mineral surfaces may be important for retention and degradation of hydrophobic pesticides in subsoils and aquifers poor in organic matter. In this work the title pyrethroids have been used to investigate selective interactions with the surfaces of four minerals. Sorption of the four pyrethroids was quantified in batch experiments with initial pyrethroid concentrations of 1–100 μg/l. Sorption to centrifuge tubes used in the batch experiments accounted for 25–60% of total sorption. Net sorption was obtained from total sorption after subtracting the amounts of pyrethroids sorbed to centrifuge tubes used. All isotherms could be fitted by the Freundlich equation with n ranging between 0.9 and 1.1. Bonding affinities per unit surface area decreased in the order: corundum>quartz>montmorillonitekaolinite. A similar sequence as found for the total surface tension of the minerals. All minerals showed the same selectivity order with respect to sorption affinity of the four pyrethroids: lambda-cyhalothrin>deltamethrin>cypermethrin>fenvalerate, which shows that the most hydrophobic compound is sorbed most strongly. Stereochemical properties of the four pyrethroid formulations may also contribute to the selectivity pattern.     

The past impact of livestock husbandry on dispersal of plant seeds in the landscape of Denmark

The recent decline in species richness in (semi)-natural habitats in northern Europe has largely been attributable to habitat destruction, and to subsequent limitation in seed dispersal among fragments. However, some habitat types were probably split up already in the historical landscape, but the segregated parts were probably not isolated to the present degree. This paper seeks evidence for livestock as vectors for propagules at 3 spatial scales in the past cultural landscape. Three main scales at which livestock acted as seed dispersers are important: free movement in the landscape (1-10 km), driving animals to mast feeding or to manors (10-50 km), and the export of living animals (hundreds of km). The emerging picture is for most plant species a dramatically decreased chance of dispersal in the modern landscape. The consequence is probably decreasing species richness in (semi)-natural plant communities, such as pasture, meadow, and heathland.     

The use of environmental metabolomics to determine glyphosate level of exposure in rapeseed (Brassica napus L.) seedlings

Metabolic profiling in plants can be used to differentiate between treatments and to search for biomarkers for exposure. A methodology for processing Ultra-High-Performance Liquid Chromatography-Diode-Array-Detection data is devised. This methodology includes a scheme for selecting informative wavelengths, baseline removal, retention time alignment, selection of relevant retention times, and principal component analysis (PCA). Plant crude extracts from rapeseed seedling exposed to sublethal concentrations of glyphosate are used as a study case. Through this approach, plants exposed to concentrations down to 5 μM could be distinguished from the controls. The compounds responsible for this differentiation were partially identified and were different from those specific for high exposure samples, which suggests that two different responses to glyphosate are elicited in rapeseed depending on the level of exposure. The PCA loadings indicate that a combination of other metabolites could be more sensitive than the response of shikimate to detect glyphosate exposure.     

Effects of preference heterogeneity among landowners on spatial conservation prioritization

The participation of private landowners in conservation is crucial to efficient biodiversity conservation. This is especially the case in settings where the share of private ownership is large and the economic costs associated with land acquisition are high. We used probit regression analysis and historical participation data to examine the likelihood of participation of Danish forest owners in a voluntary conservation program. We used the results to spatially predict the likelihood of participation of all forest owners in Denmark. We merged spatial data on the presence of forest, cadastral information on participation contracts, and individual‐level socioeconomic information about the forest owners and their households. We included predicted participation in a probability model for species survival. Uninformed and informed (included land owner characteristics) models were then incorporated into a spatial prioritization for conservation of unmanaged forests. The choice models are based on sociodemographic data on the entire population of Danish forest owners and historical data on their participation in conservation schemes. Inclusion in the model of information on private landowners’ willingness to supply land for conservation yielded at intermediate budget levels up to 30% more expected species coverage than the uninformed prioritization scheme. Our landowner‐choice model provides an example of moving toward more implementable conservation planning.     

Modelling C and N mineralization during decomposition of anaerobically digested and composted municipal solid waste.

Application of municipal solid waste (MSW) to arable land can be used to close the nutrient cycle between urban and rural areas. The aim of the current study was to quantify net N mineralization and respiration from composted MSW (CMSW) and anaerobically digested MSW (ADMSW) applied to soil, and to test whether a simple relationship between net N mineralization and respiration that was developed for plant materials, was applicable for these types of MSW. In a laboratory experiment, CMSW and ADMSW were incorporated into soil and incubated at 15 degrees C. During the 149-day experiment, netN mineralization and respiration were determined. Cumulative respiration derived from both MSW types was very steep during the first 30 days, after which it levelled off. However, calculated on the basis of applied C, the ADMSW was 10 times more degradable than the CMSW. Both MSW types caused initial net N immobilization followed by re-mineralization. A simple model based on the relationship between net N mineralization and respiration was only applicable for the MSW after significant modifications. If farmers are to recognize CMSW and ADMSW as valuable fertilizers, it is important that they can be produced with higher maturity, in order to avoid initial N immobilization.     

pH-dependent release of cadmium,copper, and lead from natural and sludge-amended soils

The pH-dependent release of cadmium, copper, and lead from soil materials was studied by use of a stirred flow cell to quantify their release and release rates, and to evaluate the method as a test for the bonding strength and potential mobility of heavy metals in soils. Soil materials from sludge-amended and nonamended A horizons from a Thai coarse-textured Kandiustult and a Danish loamy Hapludalf were characterized and tested. For each soil sample, release experiments with steady state pH values in the range 2.9 to 7.1 and duration of 7 d were performed. The effluent was continuously collected and analyzed. Release rates and total releases were higher for the Hapludalf than the Kandiustult and higher for the sludge-amended soils than the nonamended soils. With two exceptions the relative release rates (release rate/total content of metal in soil) plotted vs. steady state pH followed the same curves for each metal, indicating similar bonding strengths. These curves could be described by a rate expression of the form: relative release rate = k[H+]a, with specific a (empirical constant) and k (rate constant) parameters for each metal demonstrating that metal release in these systems can be explained by proton-induced desorption and dissolution reactions. With decreasing pH, pronounced increases in release rates were observed in the sequence cadmium > lead > copper, which express the order of metal lability in the soils. The flow cell system is useful for comparison of metal releases as a function of soil properties, and can be used as a test to rank soils with respect to heavy metal leaching.