From sewage sludge ash to a recycled feed phosphate - digestibility of precipitated calcium phosphate in broiler chickens and growing pigs.

Today, EU is largely (∼92%) dependent on the import of phosphates as most mines are located outside Europe. Because of the limited availability, phosphorus (P) is included on the list of Critical Raw Materials. Precipitated calcium phosphate (PCP) recovered from sewage sludge ash is a novel and sustainable option to replace mined P as raw material in feed phosphates, e.g. monocalcium phosphate (MCP) or dicalcium phosphate, but the digestibility has not yet been tested in vivo. The aim was therefore to determine PCP and MCP apparent ileal digestibility (AID) of P in broiler chickens and apparent (ATTD) and true (TTTD) total tract digestibility of P in growing pigs. A chicken study comprised 240 Ross 308 chickens that were housed in groups of eight from day 21 to day 28. Five diets were used, a basal diet and two test diets, which contributed either 0.075% (low) or 0.150% (high) additional P for each of the test sources (MCP and PCP). The basal and test diets were composed to achieve increasing levels of P and AID was calculated with regression analysis. In the pig study, eight individually housed pigs were used in a change-over study with two experimental periods. The pigs were fed a basal P-free diet in a preperiod to be able to estimate endogenous P losses and then two different diets in two periods using a change-over design, where MCP and PCP were the only P source, providing in total 0.33 (basal diet), 4.42 (MCP) and 3.53 (PCP) g kg-1P, respectively. The AID of P in PCP and MCP for chickens was 58.4 and 75.1% (P = 0.166). The ATTD and TTTD of P in PCP for pigs were 58.4 and 67.2%, respectively, which was lower (P < 0.001) than the corresponding values for MCP (82.1 and 89.1%), respectively. The digestibility of calcium (Ca) did not differ in the chicken diets with high inclusion levels of PCP and MCP (54.7 and 55.3%, respectively, P = 0.535), but was lower for PCP than MCP in the pig study (57.8 and 70.8% respectively, P = 0.001). In conclusion, the digestibility of P in PCP for chickens did not differ from conventional MCP, whereas for pigs, it was lower, but could be a viable alternative to other common sources of P.

Evaluation of frameworks for ecotoxicological hazard classification of waste.

A new harmonized EU regulation for the classification of waste came into effect on 1st June 2015, in which the criteria and assessment methods for the classification of hazardous waste are harmonized with other internationally agreed-upon systems for hazard classification of chemicals (CLP). However, criteria and guidance for the assessment of ecotoxicological hazard (Hazard Property 14, HP14) are still lacking for waste classification. This paper have evaluated and compared two HP14 classification frameworks: (i) a calculation method (summation) for mixtures, and (ii) leaching tests. The two frameworks were evaluated by surveying and evaluating ecotoxicological data for Cu, Zn, K and Ca species in bottom ash from incinerated waste, together with geochemical speciation modelling. Classification based on the summation method proved to be highly sensitive to the choice of speciation and ecotoxicological classification. This results in a wide range of critical concentrations triggering hazardous classification (in particular for Cu and Zn). Important parameters governing the availability of toxic elements, such as transformation from one species to another and complexation on organic or inorganic sorbents, are not accounted for. Geochemical modelling revealed that a testing strategy built on CLP based leaching tests (liquid/solid ratio (L/S)⩾10,000, pH range 5.5-8.5) avoids bias and is superior to the summation method with respect to both precision and accuracy. A testing strategy built on leaching tests, designed for risk assessment purposes, (L/S ratio of 10, natural pH of the ash) severely underestimate the hazard associated with the presence of toxic compounds (Cu and Zn), while simultaneously falsely indicate a hazardousness due to the presence of non-toxic compounds (Ca and K). However, the testing methods adopted by CLP are problematic from a practical and functional point of view. To conclude, the L/S ratio and pH were found to be critical for hazard classification based on leaching test methods. Further studies are needed to develop a relevant, practical and functional testing strategy for HP14 hazardous waste classification.

Influence of leaching conditions for ecotoxicological classification of ash.

The Waste Framework Directive (WFD; 2008/98/EC) states that classification of hazardous ecotoxicological properties of wastes (i.e. criteria H-14), should be based on the Community legislation on chemicals (i.e. CLP Regulation 1272/2008). However, harmonizing the waste and chemical classification may involve drastic changes related to choice of leaching tests as compared to e.g. the current European standard for ecotoxic characterization of waste (CEN 14735). The primary aim of the present study was therefore to evaluate the influence of leaching conditions, i.e. pH (inherent pH (∼10), and 7), liquid to solid (L/S) ratio (10 and 1000 L/kg) and particle size (<4 mm, <1 mm, and <0.125 mm), for subsequent chemical analysis and ecotoxicity testing in relation to classification of municipal waste incineration bottom ash. The hazard potential, based on either comparisons between element levels in leachate and literature toxicity data or ecotoxicity testing of the leachates, was overall significantly higher at low particle size (<0.125 mm) as compared to particle fractions <1mm and <4mm, at pH 10 as compared to pH 7, and at L/S 10 as compared to L/S 1000. These results show that the choice of leaching conditions is crucial for H-14 classification of ash and must be carefully considered in deciding on future guidance procedures in Europe.

An ecotoxicological evaluation of aged bottom ash for use in constructions.

Municipal and Industrial Solid Waste Incineration (MISWI) bottom ash is mainly deposited in landfills, but natural resources and energy could be saved if these ash materials would be used in geotechnical constructions. To enable such usage, knowledge is needed on their potential environmental impact. The aim of this study was to evaluate the ecotoxicity of leachates from MISWI bottom ash, aged for five years, in an environmental relevant way using a sequential batch leaching method at the Liquid/Solid-ratio interval 1-3, and to test the leachates in a (sub)chronic ecotoxicity test. Also, the leachates were characterized chemically and with the technique of diffusive gradients in thin films (DGTs). By comparing established ecotoxicity data for each element with chemically analysed and labile concentrations in the leachates, potentially problematic elements were identified by calculating Hazard Quotients (HQ). Overall, our results show that the ecotoxicity was in general low and decreased with increased leaching. A strong correspondence between calculated HQs and observed toxicity over the full L/S range was observed for K. However, K will likely not be problematic from a long-term environmental perspective when using the ash, since it is a naturally occurring essential macro element which is not classified as ecotoxic in the chemical legislation. Although Cu was measured in total concentrations close to where a toxic response is expected, even at L/S 3, the DGT-analysis showed that less than 50% was present in a labile fraction, indicating that Cu is complexed by organic ligands which reduce its bioavailability.

Improved understanding of key elements governing the toxicity of energy ash eluates.

Ash from incinerated waste consists mainly of a complex mixture of metals and other inorganic elements and should be classified based on its inherent hazardous effects according to EUs Waste Framework Directive. In a previous study, we classified eight eluates from ash materials from Swedish incineration plants, both chemically and ecotoxicologically (using bacteria, algae, crustacean and fish). Based on measured concentrations in the eluates together with literature acute toxicity data on the crustacean Nitocra spinipes we identified six elements (i.e. Zn, Cu, Pb, Al, K and Ca) potentially responsible for the observed ecotoxicity. However, comparing the used test methods with N. spinipes, the acute test was relatively insensitive to the eluates, whereas the (sub)chronic test (i.e. a partial life cycle test, investigating larval development ratio) was very sensitive. The overall aim of this follow-up study was to verify if the pinpointed elements could be responsible for the observed (sub)chronic toxicity of the eluates. Individual effect levels (i.e. NOEC values) for these six elements were therefore generated using the (sub)chronic test. Our results show that for six of the eight eluates, the observed ecotoxicity can be explained by individual elements not classified as ecotoxic (Al, K and Ca) according to chemical legislation. These elements will not be considered using summation models on elements classified as ecotoxic in solid material for the classification of H-14, but will have significant implications using ecotoxicological test methods for this purpose.

An ecotoxicological approach for hazard identification of energy ash.

Within the EU, ash should be classified by its inherent hazardous effects under criterion H-14 (ecotoxic) in the Directive on waste (2008/98/EC). Today, however, there are no harmonized quantitative criterions for such a classification, but it is stated that biological test systems can be used. In this study seven ash materials were leached and characterized, both biologically and chemically. The objectives were to evaluate if (a) clear concentration-response relationships could be achieved for the selected toxicity tests (bacteria, algae, crustacean and fish), (b) some test(s) are generally more sensitive and (c) the toxic responses were consistent with the chemical analyzes. Interestingly, our results indicate that high concentrations of non-hazardous components (Ca, K) influenced the toxicity of almost all ash eluates, whereas hazardous components (e.g. Zn, Pb) only influenced the toxicity of the eluates ranked as most hazardous. If considering both hazardous and non-hazardous substances, the observed toxic responses were relatively consistent with the chemical analyzes. Our results further showed that the (sub)chronic tests were much more sensitive than the acute tests. However, the use of extrapolation factors to compensate for using the less sensitive acute tests will likely lead to either over- or underestimations of toxicity. Our recommendation is therefore that classification of waste according to H-14 should be based on (sub)chronic test data. Finally, given that treatment of the eluates prior to toxicity testing has a major significance on the concentration and speciation of released substances, further studies are needed in order to propose a relevant testing scheme.