Phosphorus transformations in plant-based and bio-waste materials induced by pyrolysis

Strategies are needed to increase the sustainability of phosphorus (P) fertiliser management in agriculture. This paper reports on the potential of pyrolysis treatment to recycle P from renewable materials previously regarded as wastes. The study used K-edge X-ray absorption near-edge structure (XANES) spectroscopy to examine chemical forms of P in the waste feedstock materials and corresponding biochars (pyrolysis at 480–500 °C) of four ligno-cellulosic, plant-based residues and five relatively P-rich livestock and water-treatment by-products, to acquire information on changes in potential P fertiliser value. Pyrolysis enriched P in the biochars by factors of 1.3–4.3, thus offering wide-ranging P fertiliser potential. XANES spectroscopy revealed hydroxyapatite (HAP) as one of the dominant chemical P compounds in the feedstocks, ranging from 14% (rice husks) to 98% (animal bone) of total P. For most materials, pyrolysis increased the proportion of HAP, and pyrophosphates were generated in several cases. These alterations possibly lead to diversity in the P solubility characteristics of the biochars if used as soil amendments; this is an important property of environmentally sound P fertilisers.     

A multi-year study following BACI design reveals no short-term impact of <Emphasis Type="Italic">Bti</Emphasis> on chironomids (Diptera) in a floodplain in Eastern Austria

Short-term impacts of aerial application of Bacillus thuringiensis israelensis (Bti) on Culicidae and Chironomidae were investigated over several years in temporary waters of the Dyje and Morava floodplains in Eastern Austria. The sampling followed a Before-After-Control-Impact (BACI) approach with sampling dates immediately before and shortly after the application and was repeated for 3 years. To test for effects of the Bti treatment on the two Diptera families, linear mixed-effects models were used. Data analysis included the factors Before-After and Control-Impact as fixed effects, while general temporal and spatial variables were random effects. One hundred sixteen taxa of chironomids were identified. Abundance varied between 2 and 1125 larvae per m², while culicid densities reached values of several 100 ind. per liter. Total culicid abundance significantly decreased after the Bti treatment, whereas no significant effects were found on the abundance of total chironomids and dominant chironomid subfamilies, tribes, and genera, on relative proportions of chironomid feeding guilds, diversity, and species composition. Further studies from this area are needed to extend the investigation over a period of several weeks in order to reveal possible delayed effects of the larvicide application.     

Persistence revisited

We are happy and proud to announce that our book ‘Atmospheric Degradation of Organic Substances — Data for Persistence and Long-range Transport’ (see pp. 143–144) has recently been published by Wiley-VCH [1]. It contains a critical compilation of photo degradation rate constants and quantum efficiencies relevant for calculating the atmospheric persistence of volatile and a few semi-volatile organic compounds. In addition to the data of nearly 1100 substances, the importance of persistence in air and long-range transport potential is presented in two chapters from the point of view of chemicals legislation and of atmospheric photochemistry.     

A Multilevel Modeling Approach to Assessing Regional and Local Landscape Features for Lake Classification and Assessment of Fish Growth Rates

The ecoregion and watershed frameworks are landscape-based classifications that have been used to group waterbodies with respect to measures of community structure; however, they have yet to be evaluated for grouping lakes for demographic characteristics of fish populations. We used a multilevel modeling approach to determine if variability in mean fish length at age could be partitioned by ecoregions and watersheds. For the ecoregions analysis, we then examined if within-ecoregion variability could be explained by local water quality and lake morphometry characteristics. We used data from agency surveys conducted during 1974-1984 for age 2 and 3 fish of seven common warm and coolwater fish species. Variance in mean length at age between ecoregions for all species was not significant, and between-watershed variance estimates were only significant in 3 out of 14 analyses; however, the total amount of variation between watersheds was very small (ranging from 1.8% to 3.7% of the total variance), indicating that ecoregions and watersheds were ineffective in partitioning variability in mean length at age. Within ecoregions, water quality and lake morphometric characteristics accounted for 2%-23% of the variation in mean length at age. Measures of lake productivity were the most common significant covariates, with mean length at age increasing with increasing lake productivity. Much of the variability in mean length at age was not accounted for, suggesting that other local factors such as biotic interactions, fish density, and exploitation are important. The results indicate that the development of an effective regional framework for managing inland lakes will require a substantial effort to understand sources of demographic variability and that managers should not rely solely on ecoregions or watersheds for grouping lakes with similar growth rates.     

Effect of weathering product assemblages on Pb bioaccessibility in mine waste: implications for risk management

General assessments of orebody types and associated mine wastes with regard to their environmental signature and human health hazards are needed to help in managing present and historical mine waste facilities. Bioaccessibility tests and mineralogical analysis were carried out on mine waste from a systematic sampling of mine sites from the Central Wales orefield, UK. The bioaccessible Pb widely ranged from 270 to 20,300 mg/kg (mean 7,250 mg/kg, median 4,890 mg/kg), and the bioaccessible fraction from 4.53 to >100 % (mean 33.2 %, median 32.2 %), with significant (p?=?0.001) differences among the mine sites. This implies sensitivity of bioaccessibility to site-specific conditions and suggests caution in the use of models to assess human health impacts generalised on the basis of the mineral deposit type. Mineralogical similarities of the oxidation products of primary galena provided a better control over the observed Pb bioaccessibility range. The higher Pb bioaccessibility (%) was related to samples containing cerussite, irrespective of the presence of other Pb minerals in the mineral assemblage; lower Pb bioaccessibility resulted where anglesite was the main Pb mineral phase and cerussite was absent. A solubility diagram for the various Pb minerals in the waste was derived using PHREEQC model, and the experimental Pb concentrations, measured in the simulated gastric solution, were compared with the equilibrium modelling results. For samples containing cerussite, the model well predicted the soluble Pb concentrations measured in the gastric solution, indicative of the carbonate mineral phase control on the Pb in solution for these samples and little kinetic control on the dissolution of cerussite. On the contrary, most mine waste samples containing dominant anglesite and or plumbojarosite (no cerussite) had lower solution Pb values, falling at or below the anglesite and plumbojarosite solubility equilibrium concentrations, implying kinetic or textural factors hindering the dissolution.     

Compact fluorescent lights and the impact of convenience and knowledge on household recycling rates

Increased energy costs, social marketing campaigns, public subsidies, and reduced retail prices have dramatically increased the number of compact fluorescent lights (CFLs) installed worldwide. CFLs provide many benefits, but they contain a very small amount of mercury. Given the billions of CFLs in use worldwide, they represent a significant source of mercury unless CFLs are recycled and the mercury recovered in an environmentally sound manner. In the state of Maine (northeast United States), despite mandated recycling of CFLs and availability of free CFL recycling, the household CFL recycling rate is very low. A study was undertaken to identify the primary factors responsible for low recycling. The first step was to survey householders who use CFLs. The 520 survey responses indicated that insufficient knowledge regarding recycling and inconvenience of the collection system are the two primary factors for the low recycling rate. To validate these findings, the second step was an examination of the current collection system to assess (a) the knowledge requirements necessary for recycling and (b) the convenience of the collection system. The results of this examination validated that knowledge requirements were excessively difficult to fulfill and the collection system is not sufficiently convenient. Based on these results, waste managers should focus on increasing convenience and simplifying access to information when designing or improving household collection and recycling of CFLs.     

Limitations for heavy metal release during thermo-chemical treatment of sewage sludge ash

Phosphate recycling from sewage sludge can be achieved by heavy metal removal from sewage sludge ash (SSA) producing a fertilizer product: mixing SSA with chloride and treating this mixture (eventually after granulation) in a rotary kiln at 1000 ± 100 °C leads to the formation of volatile heavy metal compounds that evaporate and to P-phases with high bio-availability. Due to economical and ecological reasons, it is necessary to reduce the energy consumption of this technology. Generally, fluidized bed reactors are characterized by high heat and mass transfer and thus promise the saving of energy. Therefore, a rotary reactor and a fluidized bed reactor (both laboratory-scale and operated in batch mode) are used for the treatment of granulates containing SSA and CaCl₂. Treatment temperature, residence time and - in case of the fluidized bed reactor - superficial velocity are varied between 800 and 900 °C, 10 and 30 min and 3.4 and 4.6 m s⁻¹. Cd and Pb can be removed well (>95 %) in all experiments. Cu removal ranges from 25% to 84%, for Zn 75-90% are realized. The amount of heavy metals removed increases with increasing temperature and residence time which is most pronounced for Cu.In the pellet, three major reactions occur: formation of HCl and Cl₂ from CaCl₂; diffusion and reaction of these gases with heavy metal compounds; side reactions from heavy metal compounds with matrix material. Although, heat and mass transfer are higher in the fluidized bed reactor, Pb and Zn removal is slightly better in the rotary reactor. This is due the accelerated migration of formed HCl and Cl₂ out of the pellets into the reactor atmosphere. Cu is apparently limited by the diffusion of its chloride thus the removal is higher in the fluidized bed unit.     

Managing biosolids runoff phosphorus using buffer strips enhanced with drinking water treatment residuals

Vegetated buffers strips typically have limited ability to reduce delivery of dissolved phosphorus (DP) from agricultural fields to surface waters. A field study was conducted to evaluate the ability of buffer strips enhanced with drinking water treatment residuals (WTRs) to control runoff P losses from surface-applied biosolids characterized by high water-extractable P (4 g kg(-)(1)). Simulated rainfall (62.4 mm h(-1)) was applied to grassed plots (3 m x 10.7 m including a 2.67 m downslope buffer) surface-amended with biosolids at 102 kg P ha(-1) until 30 min of runoff was collected. With buffer strips top-dressed with WTR (20 Mg ha(-1)), runoff total P (TP = 2.5 mg L(-1)) and total DP (TDP = 1.9 mg L(-1)) were not statistically lower (alpha = 0.05) compared to plots with unamended grass buffers (TP = 2.7 mg L(-1); TDP = 2.6 mg L(-1)). Although the applied WTR had excess capacity (Langmuir P maxima of 25 g P kg(-1)) to sorb all runoff P, kinetic experiments suggest that sheet flow travel time across the buffers ( approximately 30 s) was insufficient for significant P reduction. Effective interception of dissolved P in runoff water by WTR-enhanced buffer strips requires rapid P sorption kinetics and hydrologic flow behavior ensuring sufficient runoff residence time and WTR contact in the buffer. Substantial phosphate-adsorbent contact opportunity may be more easily achieved by incorporating WTRs into P-enriched soils or blending WTRs with applied P sources.     

Immersed solid phase microextraction to measure chemical activity of lipophilic organic contaminants in fatty tissue samples

It is known that solid phase microextraction (SPME) fibers can be equilibrated directly within environmental matrices such as water, sediment and soil slurries. Here it is shown that this method can also be applied to biological tissue. SPME extraction of biological matrices reportedly causes lipophilic fouling of the fiber. However, we found no significant measurement bias when combining equilibrium sampling with fiber surface cleaning. The uptake of lipophilic organic pollutants from the tissue and into the SPME fiber coating was characterized by fast equilibrium partitioning without sample depletion and without impacting the sorptive properties of the fiber. The precision of the method when applied to hexachlorobenzene and several PCB congeners in harbor porpoise blubber was 15%, which includes the variation between SPME samplings, manual injections and the instrumental analysis. A good correlation (r(2)=0.95) was obtained between SPME measurements of PCB 153 in blubber and concentrations obtained via a traditional analytical approach. These results indicate that SPME is a promising technique for measuring chemical activity in biological tissue, which would make it a useful tool for studying chemical distribution in organisms as well as biodilution and biomagnification phenomena.