Leaching of cyanogenic glucosides and cyanide from white clover green manure

Use of crops for green manure as a substitute for chemical fertilizers and pesticides is an important approach towards more sustainable agricultural practices. Green manure from white clover is rich in nitrogen but white clover also produces the cyanogenic glucosides (CGs) linamarin and lotaustralin; CGs release toxic hydrogen cyanide (HCN) upon hydrolysis which may be utilized for pest control. We demonstrate that applying CGs in the form of a liquid extract of white clover to large columns of intact agricultural soils can result in leaching of toxic cyanide species to a depth of at least 1m. Although degradation of the CGs during leaching proceeded with half lives in the interval 1.5-35 h depending on soil characteristics, a fraction of the applied CGs (0.9-3.2%) was recovered in the leachate as either CGs or toxic cyanide species. Detoxification of the HCN formed was rapid in soil and leachate from both sandy and loamy soil. However, 30% of the leachate samples exceeded the EU threshold value of 50 micrgl(-1) total cyanide for drinking water and 85% exceeded the US threshold of 5 micrgl(-1) for cyanide chronic ecotoxicity in fresh water. This study demonstrates that even easily degradable natural products present in crop plants as defense compounds pose a threat to the quality of groundwater and surface waters. This aspect needs consideration in assessment of the risk associated with use of crops as green manure to replace chemical fertilizers and pesticides as well as in genetic engineering approaches to design crops with improved pest resistance.     

Elemental mobility in sulfidic mine tailings reclaimed with paper mill by-products as sealing materials

Environmental Science and Pollution Research - Sealing layers made of two alkaline paper mill by-products, fly ash and green liquor dregs, were placed on top of 50-year-old sulfide-containing...     

Integrated evaluation of the performance of a more than seven year old permeable reactive barrier at a site contaminated with chlorinated aliphatic hydrocarbons (CAHs)

An important issue of concern for permeable reactive iron barriers is the long-term efficiency of the barriers due to the long operational periods required. Mineral precipitation resulting from the anaerobic corrosion of the iron filings and bacteria present in the barrier may play an important role in the long-term performance. An integrated study was performed on the Vapokon permeable reactive barrier (PRB) in Denmark by groundwater and iron core sample characterization. The detailed field groundwater sampling carried out from more than 75 well screens up and downstream the barrier showed a very efficient removal (>99%) for the most important CAHs (PCE, TCE and 1,1,1-TCA). However, significant formation of cis-DCE within the PRB resulted in an overall insufficient efficiency for cis-DCE removal. The detailed analysis of the upstream groundwater revealed a very heterogeneous spatial distribution of contaminant loading into the PRB, which resulted in that only about a quarter of the barrier system is treating significant loads of CAHs. Laboratory batch experiments using contaminated groundwater from the site and iron material from the core samples revealed that the aged iron material performed equally well as virgin granular iron of the same type based on determined degradation rates despite that parts of the cored iron material were covered by mineral precipitates (especially iron sulfides, carbonate green rust and aragonite). The PCR analysis performed on the iron core samples indicated the presence of a microbial consortium in the barrier. A wide range of species were identified including sulfate and iron reducing bacteria, together with Dehalococcoides and Desulfuromonas species indicating microbial reductive dehalogenation potential. The microbes had a profound effect on the performance of the barrier, as indicated by significant degradation of dichloromethane (which is typically unaffected by zero valent iron) within the barrier.     

Revising REACH guidance on information requirements and chemical safety assessment for engineered nanomaterials for aquatic ecotoxicity endpoints: recommendations from the EnvNano project

The European Chemical Agency (ECHA) is in the process of revising its guidance documents on how to address the challenges of ecotoxicological testing of nanomaterials. In these revisions, outset is taken in the hypothesis that ecotoxicological test methods, developed for soluble chemicals, can be made applicable to nanomaterials. European Research Council project EnvNano—Environmental Effects and Risk Evaluation of Engineered, which ran from 2011 to 2016, took another outset by assuming that: “The behaviour of nanoparticles in suspension is fundamentally different from that of chemicals in solution”. The aim of this paper is to present the findings of the EnvNano project and through these provide the scientific background for specific recommendations on how ECHA guidance could be further improved. Key EnvNano findings such as the need to characterize dispersion and dissolution rates in stock and test media have partially been addressed in the updated guidance. However, it has to be made clear that multiple characterization methods have to be applied to describe state of dispersion and dissolution over time and for various test concentration. More detailed information is called for on the specific characterization methods and techniques available and their pros and cons. Based on findings in EnvNano, we recommend that existing algal tests are supplemented with tests where suspensions of nanomaterials are aged for 1–3 days for nanomaterials that dissolve in testing media. Likewise, for daphnia tests we suggest to supplement with tests where (a) exposure is shortened to a 3 h pulse exposure in daphnia toxicity tests with environmentally hazardous metal and metal oxide nanomaterials prone to dissolution; and (b) food abundance is three to five times higher than normal, respectively. We further suggest that the importance of considering the impact of shading in algal tests is made more detailed in the guidance and that it is specified that determination of uptake, depuration and trophic transfer of nanomaterials for each commercialized functionalization of the nanomaterials is required. Finally, as an outcome of the project a method for assessing the regulatory adequacy of ecotoxicological studies of nanomaterials is proposed.     

Enzymatic processing of municipal solid waste

The focus of this work was to investigate an enzymatic liquefaction of MSW organics, paper and cardboard. Liquefaction trials were conducted in different trial volumes: 50 g lab-scale trials and 50 kg vessel-tests and evaluated based on particle size and viscosity. The viscosity results showed that Celluclast 1.5 L had the singular significant effect on liquefaction of model MSW. No effect of α-amylase, protease and interaction in between and with cellulases on viscosity and particle size distribution was found in this study. Degradable material with a particle size above 1 mm after treatment was evaluated using SEM microscopy. These results showed that paper particles were the main obstacles needing additional treatment in order to become fully liquefied. In a pilot scale test treating authentic MSW; more than 90% of initial organic and paper dry matter (DM) was recovered as liquid slurry after sieving through a 5-mm sieve. These tests were performed at up to 35% DM, showing that this process can easily manage high DM loadings. MSW enzymatic liquefaction promotes the separation of organics and paper from solids, which facilitate the use of these degradable fractions, with minimal loss, capable to enter a biogas plant through existing pipes.     

On the decline of ground lichen forests in the Swedish boreal landscape: Implications for reindeer husbandry and sustainable forest management

Lichens are a bottleneck resource for circumpolar populations of reindeer, and as such, for reindeer husbandry as an indigenous Sami land-use tradition in northern Sweden. This study uses ground lichen data and forest information collected within the Swedish National Forest Inventory since 1953, on the scale of northern Sweden. We found a 71 % decline in the area of lichen-abundant forests over the last 60 years. A decline was observed in all regions and age classes and especially coincided with a decrease of >60 year old, open pine forests, which was the primary explanatory factor in our model. The effects of reindeer numbers were inconclusive in explaining the decrease in lichen-abundant forest. The role that forestry has played in causing this decline can be debated, but forestry can have a significant role in reversing the trend and improving ground lichen conditions.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-015-0759-0) contains supplementary material, which is available to authorized users.     

Application of a contaminant mass balance method at an old landfill to assess the impact on water resources

Old and unlined landfill sites pose a risk to groundwater and surface water resources. While landfill leachate plumes in sandy aquifers have been studied, landfills in clay till settings and their impact on receiving water bodies are not well understood. In addition, methods for quantitatively linking soil and groundwater contamination to surface water pollution are required. This paper presents a method which provides an estimate of the contaminant mass discharge, using a combination of a historical investigation and contaminant mass balance approach. The method works at the screening level and could be part of a risk assessment. The study site was Risby Landfill, an old unlined landfill located in a clay till setting on central Zealand, Denmark. The contaminant mass discharge was determined for three common leachate indicators: chloride, dissolved organic carbon and ammonium. For instance, the mass discharge of chloride from the landfill was 9.4 ton/year and the mass discharge of chloride to the deep limestone aquifer was 1.4 ton/year. This resulted in elevated concentrations of leachate indicators (chloride, dissolved organic carbon and ammonium) in the groundwater. The mass discharge of chloride to the small Risby Stream down gradient of the landfill was approximately 31 kg/year. The contaminant mass balance method worked well for chloride and dissolved organic carbon, but the uncertainties were elevated for ammonium due to substantial spatial variability in the source composition and attenuation processes in the underlying clay till.     

Degradability of aged aquatic suspensions of C60 nanoparticles

In this study, aged aqueous suspensions of C(60) (nC(60)) were investigated in the respirometric OECD test for ready biodegradability. Two suspensions of nC(60) were prepared by stirring and aged under indirect exposure to sunlight for 36 months. ATR-FTIR analyses confirmed the presence of C(60)-structures in the suspensions. Samples of the nC(60) suspensions (20mg/l) were inoculated with activated sludge (30 mgTSS/L) and incubated in a mineral medium under aerobic conditions. Since no mineralisation of nC(60) was observed after 28 days of incubation, 5mg/l sodium acetate was added to the media. After additional 20 days, no mineralisation of nC(60) was observed. However, within a few days sodium acetate was completely mineralised, showing that the biomass was not inhibited by the presence of nC(60). Based on results from this simple approach, aged nC(60) can be classified as not ready biodegradable according to the standard OECD test procedure.