Granulation and calcination of alum sludge for the development of a phosphorus adsorbent: From lab scale to pilot scale.

Alum sludge, an Al-oxyhydroxide rich waste product from water treatment practices, has the potential to be valorized as a P adsorbent material. However, several challenges currently prevent its application as an adsorbent in industrial setting, i.e. a limited P adsorption capacity due to saturation by organic matter and a fine nature resulting in percolation problems in adsorption bed setups. In this study, granulation and subsequent calcination of alum sludge were proposed to overcome these issues and to improve the P adsorption properties of alum-based adsorbent (ABA) materials. The effect of calcination temperature on the physicochemical properties of granular material was examined using X-ray diffraction, mass-spectroscopy coupled thermogravimetric analysis, Fourier-transform infrared spectrometry and specific surface area analysis, combined with density and crushing strength measurements. The ABA material obtained at 550 °C showed superior P adsorption properties and, therefore, this material was selected for further P adsorption testing and characterization (scanning electron microscopy and sieving). Batch P adsorption tests showed that this material had a maximum P adsorption capacity of 7.27 mg-P g-1. Kinetic adsorption tests determined the effect of the solid-to-liquid ratio and the granule particle size on the P removal. Finally, the performance of the ABA-550 material was tested in a pilot-scale adsorption setup, using a surface water stream (0.47 mg-P L-1) at a flow rate of 200 L h-1. During the test, the P removal efficiency always exceeded 86%, while the material maintained its structural stability. The results of this study illustrate the potential of granulated/calcined ABA materials for P adsorption, paving the way for the industrial application of this novel, sustainable P removal technology.

Carbonation is affecting biodegradability testing of fiber cement composites.

Fiber cement composites (FCCs) containing natural cellulosic fibres are emerging materials in the building industry. At the end of life, FCCs are often disposed of as part of the C&DW in a landfill. The production of landfill gasses in landfills needs to be kept as low as possible. Generally, leaching of total dissolved organic carbon (DOC) is used as a proxy for the biodegradability of a waste material and the subsequent production of landfill gasses, and is, therefore, used to evaluate biodegradability of waste. In this study, FCC samples with varying average diameter and varying age were subjected to both a batch leaching test (determine DOC leaching) and to a standardized biodegradability test. The batch leaching showed that the DOC leaching ranged between 520 and 1300 mg kg-1 for the tested samples, and that leaching of DOC decreases with increasing particle diameter and with increasing effects of ageing. Yet, the biodegradability results indicated that the leaching of DOC from FCCs does not result in the release of landfill gasses. This study hypothises that the DOC that leaches from the FCCs is being degraded to CO2, but that the formed CO2 is immediately captured by the material itself through the process of carbonation. An inpermeable layer is formed around the material that stops further leaching of DOC. The results of this study therefore suggest that leaching of DOC is a poor indicator for the biodegradability of FCCs.

Microwave Radiation as a Pre-Treatment for Standard and Innovative Fragmentation Techniques in Concrete Recycling.

Recent advances in concrete recycling technology focus on novel fragmentation techniques to obtain aggregate fractions with low cement matrix content. This study assesses the aggregate liberation effectiveness of four different treatment processes including standard and innovative concrete fragmentation techniques. Lab-made concrete samples were subjected to either standard mechanical crushing technique (SMT) or electrodynamic fragmentation (EDF). For both fragmentation processes, the influence of a microwave weakening pre-treatment technique (MWT) was investigated. A detailed analysis of the particle size distribution was carried out on samples after fragmentation. The >5.6 mm fraction was more deeply characterized for aggregate selective liberation (manual classification to separate liberated aggregates) and for cement matrix content (thermogravimetric measurements). Results highlight that EDF treatment is more effective than SMT treatment to selectively liberate aggregates and to decrease the cement matrix content of the >5.6 mm fraction. EDF fully liberates up to 37 wt.% of the >5.6 mm natural aggregates, while SMT only liberates 14⁻16 wt.%. MWT pre-treatment positively affects aggregate liberation and cement matrix removal only if used in combination with SMT; no significant effect in combination with EDF was recorded. These results of this study can provide insights to successfully implement innovative technology in concrete recycling plants.

Round robin testing of a percolation column leaching procedure.

Round robin test results of a percolation column leaching procedure (CEN/TS 14405:2004), organised by the Flemish Institute for Technological Research (VITO), over a time span of 13years with a participation of between 8 and 18 different laboratories are presented and discussed. Focus is on the leachability of heavy metals As, Cd, Cr, Cu, Hg, Ni, Pb and Zn from mineral waste materials. By performing statistical analyses on the obtained results, insight into the reproducibility and repeatability of the column leaching test is gathered. A ratio of 1:3 between intra- and inter-laboratory variability is found. The reproducibility of the eluates' element concentrations differ significantly between elements, materials and fractions (i.e. different liquid-to-solid ratios). The reproducibility is discussed in light of the application of the column leaching test for legal and environmental policy purposes. In addition, the performances of laboratories are compared.

Extent of copper tolerance and consequences for functional stability of the ammonia-oxidizing community in long-term copper-contaminated soils.

Adaptation of soil microbial communities to elevated copper (Cu) concentrations has been well documented. However, effects of long-term Cu exposure on adaptation responses associated with functional stability and structural composition within the nitrifying community are still unknown. Soils were sampled in three field sites (Denmark, Thailand, and Australia) where Cu gradients had been established from 3 to 80 years prior to sampling. In each field site, the potential nitrification rate (PNR) decreased by over 50% with increasing soil Cu, irrespective of a 20 to >200-fold increase in Cu tolerance (at the highest soil Cu) among the nitrifying communities. This increased tolerance was associated with decreasing numbers (15-120-fold) of ammonia-oxidizing bacteria (AOB), except in the oldest contaminated field site, decreasing numbers of ammonia-oxidizing archaea (AOA; 10-130-fold) and differences in the operational taxonomic unit (OTU) composition of the AOB and, to a lesser extent, AOA communities. The sensitivity of nitrifying communities, previously under long-term Cu exposure, to additional stresses was assessed. Nitrification in soils from the three field sites was measured following acidification, pesticide addition, freeze-thaw cycles, and dry-rewetting cycles. Functional stability of the nitrification process was assessed immediately after stress application (resistance) and after an additional three weeks of incubation (resilience). No indications were found that long-term Cu exposure affected the sensitivity to the selected stressors, suggesting that resistance and resilience were unaffected. It was concluded that the nitrifying community changed structurally in all long-term Cu-exposed field sites and that these changes were associated with increased Cu tolerance but not with a loss of functional stability.

Bioavailability of zinc and copper in biosolids compared to their soluble salts.

For essential elements, such as copper (Cu) and zinc (Zn), the bioavailability in biosolids is important from a nutrient release and a potential contamination perspective. Most ecotoxicity studies are done using metal salts and it has been argued that the bioavailability of metals in biosolids can be different to that of metal salts. We compared the bioavailability of Cu and Zn in biosolids with those of metal salts in the same soils using twelve Australian field trials. Three different measures of bioavailability were assessed: soil solution extraction, CaCl(2) extractable fractions and plant uptake. The results showed that bioavailability for Zn was similar in biosolid and salt treatments. For Cu, the results were inconclusive due to strong Cu homeostasis in plants and dissolved organic matter interference in extractable measures. We therefore recommend using isotope dilution methods to assess differences in Cu availability between biosolid and salt treatments.

Biological and chemical assessments of zinc ageing in field soils.

As zinc (Zn) is both an essential trace element and potential toxicant, the effects of Zn fixation in soil are of practical significance. Soil samples from four field sites amended with ZnSO(4) were used to investigate ageing of soluble Zn under field conditions over a 2-year period. Lability of Zn measured using (65)Zn radioisotope dilution showed a significant decrease over time and hence evidence of Zn fixation in three of the four soils. However, 0.01 M CaCl(2) extractions and toxicity measurements using a genetically modified lux-marked bacterial biosensor did not indicate a decrease in soluble/bioavailable Zn over time. This was attributed to the strong regulatory effect of abiotic properties such as pH on these latter measurements. These results also showed that Zn ageing occurred immediately after Zn spiking, emphasising the need to incubate freshly spiked soils before ecotoxicity assessments.

Bacteria, not archaea, restore nitrification in a zinc-contaminated soil.

Biological ammonia oxidation had long been thought to be mediated solely by discrete clades of beta- and gamma-proteobacteria (ammonia-oxidizing bacteria; AOB). However, ammonia-oxidizing Crenarchaeota (ammonia-oxidizing archaea; AOA) have recently been identified and proposed to be the dominant agents of ammonia oxidation in soils. Nevertheless, the dynamics of AOB versus AOA, and their relative contribution to soil ammonia oxidation and ecosystem functioning on stress and environmental perturbation, remain unknown. Using a 3-year longitudinal field study and the amoA gene as a molecular marker, we demonstrate that AOB, but not AOA, mediate recovery of nitrification after zinc (Zn) contamination. Pristine soils showed approximately equal amoA gene copy numbers and transcript levels for AOB and AOA. At an intermediate Zn dose (33.7 mmol Zn per kg), ammonia oxidation was completely inhibited, and the numbers of AOB and AOA amoA gene copies and gene transcripts were reduced. After 2 years, ammonia oxidation in the field soils was fully restored to preexposure levels, and this restoration of function was concomitant with an increase of AOB amoA gene copy and gene transcript numbers. Analysis of the restored community revealed domination by a phylogenetically distinct Zn-tolerant Nitrosospira sp. community. In contrast, the numbers of AOA amoA gene copies and gene transcripts remained 3- and 10(4)-fold lower than recovered AOB values, respectively. Thus, although recent findings have emphasized a dominant role of archaea in soil-borne ammonia oxidation, we demonstrate that a phylogenetic shift within the AOB community drives recovery of nitrification from Zn contamination in this soil.

White clover nodulation index in heavy metal contaminated soils- a potential bioindicator.

The morphological effects of heavy metal stress on the nodulation ability of Rhizobium spp. and growth of white clover (Trifolium repens L.) were studied in the laboratory under controlled conditions. Fourteen topsoils were collected from an area with elevated metal concentrations (Cd, Zn, and Pb). White clover was cultivated using a specialized "rhizotron" method to observe the development of root and nodule characteristics. Results show effects of increasing heavy metal concentrations on nodulation development, especially the nodulation index (i.e., the number of nodules per gram of the total fresh biomass). A significant decrease in nodulation index was observed at about 2.64 mg Cd kg(-1), 300 mg Zn kg(-1), and 130 mg Pb kg(-1) in these soils. The sensitivity of the nodulation index in relation to other morphological characteristics is discussed further. It is proposed that the nodulation index of white clover is a suitable bioindicator of increased heavy metal concentrations in soil.

Application of phytotoxicity data to a new Australian soil quality guideline framework for biosolids.

To protect terrestrial ecosystems and humans from contaminants many countries and jurisdictions have developed soil quality guidelines (SQGs). This study proposes a new framework to derive SQGs and guidelines for amended soils and uses a case study based on phytotoxicity data of copper (Cu) and zinc (Zn) from field studies to illustrate how the framework could be applied. The proposed framework uses normalisation relationships to account for the effects of soil properties on toxicity data followed by a species sensitivity distribution (SSD) method to calculate a soil added contaminant limit (soil ACL) for a standard soil. The normalisation equations are then used to calculate soil ACLs for other soils. A soil amendment availability factor (SAAF) is then calculated as the toxicity and bioavailability of pure contaminants and contaminants in amendments can be different. The SAAF is used to modify soil ACLs to ACLs for amended soils. The framework was then used to calculate soil ACLs for copper (Cu) and zinc (Zn). For soils with pH of 4-8 and OC content of 1-6%, the ACLs range from 8 mg/kg to 970 mg/kg added Cu. The SAAF for Cu was pH dependant and varied from 1.44 at pH 4 to 2.15 at pH 8. For soils with pH of 4-8 and OC content of 1-6%, the ACLs for amended soils range from 11 mg/kg to 2080 mg/kg added Cu. For soils with pH of 4-8 and a CEC from 5-60, the ACLs for Zn ranged from 21 to 1470 mg/kg added Zn. A SAAF of one was used for Zn as it concentrations in plant tissue and soil to water partitioning showed no difference between biosolids and soluble Zn salt treatments, indicating that Zn from biosolids and Zn salts are equally bioavailable to plants.

Models for the field-based toxicity of copper and zinc salts to wheat in 11 Australian soils and comparison to laboratory-based models.

Laboratory-based relationships that model the phytotoxicity of metals using soil properties have been developed. This paper presents the first field-based phytotoxicity relationships. Wheat (Triticum aestivum L.) was grown at 11 Australian field sites at which soil was spiked with copper (Cu) and zinc (Zn) salts. Toxicity was measured as inhibition of plant growth at 8 weeks and grain yield at harvest. The added Cu and Zn EC10 values for both endpoints ranged from approximately 3 to 4760 mg/kg. There were no relationships between field-based 8-week biomass and grain yield toxicity values for either metal. Cu toxicity was best modelled using pH and organic carbon content while Zn toxicity was best modelled using pH and the cation exchange capacity. The best relationships estimated toxicity within a factor of two of measured values. Laboratory-based phytotoxicity relationships could not accurately predict field-based phytotoxicity responses.

Modeling the toxicity of copper and zinc salts to wheat in 14 soils.

Interest is mounting in developing and utilizing soil-specific soil quality guidelines. This requires quantifying the effects that soil physicochemical properties have on various ecotoxicological endpoints, including phytotoxicity. To this end, 14 agricultural soils from Australia with differing soil properties were spiked with copper (Cu) and zinc (Zn) salts and used to conduct 21-d plant growth inhibition tests using wheat (Triticum aestivum L.) in pot trials. The toxicity of Cu and Zn was similar with 10% effect concentration (EC10) values ranging from 110 to 945 and from 235 to 965 mg/kg, respectively, while the corresponding median effect concentration (EC50) values ranged from 240 to 1,405 and 470 to 1,745 mg/kg, respectively. Copper toxicity values (EC10, EC20, and EC50) were best modeled by the logarithm of cation exchange capacity (CEC) and either soil pH or electrical conductivity. Zinc EC50 and EC20 values were best modeled using the logarithm of CEC, while the EC10 data were best modeled using soil pH and the logarithm of organic carbon. These models generally estimated toxicity within a factor of two of the measured values.

Soil factors controlling the toxicity of copper and zinc to microbial processes in Australian soils.

Abstract-Two soil microbial processes, substrate-induced nitrification (SIN) and substrate-induced respiration (SIR), were measured in the topsoils of 12 Australian field trials that were amended separately with increasing concentrations of ZnSO4 or CuSO4. The median effect concentration (EC50) values for Zn and Cu based on total metal concentrations varied between 107 and 8,298 mg kg(-1) for Zn and 108 and 2,155 mg kg(-1) Cu among soils. The differences in both Zn and Cu toxicity across the 12 soils were not explained by either the soil solution metal concentrations or CaCl2-extractable metal concentrations, because the variation in the EC50 values was larger than those using total concentrations. Toxicity of Zn and Cu decreased with increasing soil pH for SIN. For Cu, also increasing cation exchange capacity (CEC) and percent clay decreased the toxicity towards SIN. In contrast to SIN, soil pH had no significant effect on toxicity values of SIR. Significant relationships were found between the EC50 values for SIR and background Zn and CEC for Zn, and percent clay and log CEC for Cu. Relationships such as those developed in this study will permit Australian environmental regulation to move from single-value national soil quality guidelines to soil-specific quality guidelines and permit soil-specific risk assessments to be undertaken.

Tolerance of nitrifying bacteria to copper and nickel.

Evidence is mounting that soil microorganisms can become increasingly tolerant to metals on exposure. However, in situ investigations regarding the effects of metals, particularly Cu and Ni, on specific soil functions/communities are still limited in number. Here, we investigated whether preexposure of nitrifying bacteria to Cu or Ni can induce increased tolerance to these metals. We also investigated whether changes in the tolerance of populations exposed to Cu under field conditions (long term) or in a laboratory-spiked soil (short term) occur. The method used was specifically designed to avoid possible confounding factors because of aging of metals in soil. Sterilized soils were enriched with different concentrations of Ni or Cu and were inoculated with the same soil that was either uncontaminated or had been contaminated previously with metals. Nitrification was measured after 28 d. In the laboratory-spiked soil, the exposed nitrifier community showed an increased tolerance to Ni but not to Cu. However, we found an increased tolerance to Cu in the case of a nitrifying community exposed to Cu for nearly 80 years under field conditions. These results indicate that the capacity of nitrifying bacteria to adapt to at least some metals is a widespread phenomenon. However, acquisition of tolerance to Cu may be more difficult, or require more time, compared with tolerance to Ni.

Toxicity of heavy metals in soil assessed with various soil microbial and plant growth assays: a comparative study.

Abstract-Elevated metal concentrations in soils can disturb the soil ecosystem; thus, researchers strive to identify the most sensitive assay for detection of the early signs of toxicity. The purpose of the present study was to compare eight different ecotoxicological endpoints on the same set of metal-contaminated soils that were collected from seven series of soils sampled during field trials. The endpoints are based on three microbial assays (potential nitrification rate [PNR], substrate-induced respiration [SIR], and basal respiration [BR]) and two plant growth tests, one of which included symbiotic N fixation. The overall sensitivity of the endpoints to detect statistically significant adverse effects ranked as follows: PNR > SIR (lag time) > plant yield and N fixation > SIR (respiration after 24 and 48 h) > BR. The lowest adverse effect concentrations were found with the PNR at 7 mg kg(-1) of Cd and 107 mg kg(-1) of Zn. The variability of these endpoints among different uncontaminated soils was additionally assessed on 14 soil samples. That variability showed a strong correlation with sensitivity scores, illustrating that metal-sensitive endpoints have a large natural variability. We question the ecological relevance of highly sensitive microbial assays, because they tend to have a large natural variability. The identification of toxicity in the field requires endpoints that are highly sensitive and that do not vary greatly among soils (i.e., robust); however, no such endpoint was found in the present study. The endpoints that combined average sensitivity and robustness were SIR (lag time), clover yield, and N fixation in clover.