Utilization and recycling of wood ashes from industrial heat and power plants regarding fertilizer use.

To achieve a sustainable circular economy for wood ash, the reuse of wood ash in agriculture and forestry is important. To evaluate the usability of ash from the combustion of natural as well as waste wood for application as fertilizer, wood fuel and corresponding ash fraction samples (n = 86) of four industrial wood-fired heat and power plants (>20 MW) were investigated. In different ash fractions, the concentrations of heavy metals (As, Cd, Pb, Ni, Tl, Zn) and plant nutrients (N, P, K, Ca) were assessed with regard to relevant legislation from the European Union and from selected European countries (Germany, Austria and Finland). Depending on fuel composition and combustion kinetics within the respective plants, the investigated ash fractions showed a wide range of nutrient and heavy metal contents. Apart from N which is mainly emitted with the flue gas, plant nutrients were present in substantial concentrations with mean values corresponding to 20% P, 55 % K and >95% Ca content compared to nutrient compound fertilizer. A direct application of most ash fractions from both natural and waste wood combustion is however not possible due to high contents of Cd, Pb and Ni. In order to develop the ash for secondary use, investigation for a suitable treatment process is necessary. An estimation of the nutrient recovery potential from industrial wood energy plants in southwest Germany showed that approx. 3.1% (P), 7.5% (K) and 22.8% (Ca) of raw material for fertilizers could be substituted by ash.

Biogeochemical Niches of Fe-Cycling Communities Influencing Heavy Metal Transport along the Rio Tinto, Spain.

In the mining-impacted Rio Tinto, Spain, Fe-cycling microorganisms influence the transport of heavy metals (HMs) into the Atlantic Ocean. However, it remains largely unknown how spatial and temporal hydrogeochemical gradients along the Rio Tinto shape the composition of Fe-cycling microbial communities and how this in turn affects HM mobility. Using a combination of DNA- and RNA-based 16S rRNA (gene) amplicon sequencing and hydrogeochemical analyses, we explored the impact of pH, Fe(III), Fe(II), and Cl- on Fe-cycling microorganisms. We showed that the water column at the acidic (pH 2.2) middle course of the river was colonized by Fe(II) oxidizers affiliated with Acidithiobacillus and Leptospirillum. At the upper estuary, daily fluctuations of pH (2.7 to 3.7) and Cl- (6.9 to 16.6 g/L) contributed to the establishment of a unique microbial community, including Fe(II) oxidizers belonging to Acidihalobacter, Marinobacter, and Mariprofundus, identified at this site. Furthermore, DNA- and RNA-based profiles of the benthic community suggested that acidophilic and neutrophilic Fe(II) oxidizers (e.g., Acidihalobacter, Marinobacter, and Mariprofundus), Fe(III) reducers (e.g., Thermoanaerobaculum), and sulfate-reducing bacteria drive the Fe cycle in the estuarine sediments. RNA-based relative abundances of Leptospirillum at the middle course as well as abundances of Acidihalobacter and Mariprofundus at the upper estuary were higher than DNA-based results, suggesting a potentially higher level of activity of these taxa. Based on our findings, we propose a model of how tidal water affects the composition and activity of the Fe-cycling taxa, playing an important role in the transport of HMs (e.g., As, Cd, Cr, and Pb) along the Rio Tinto. IMPORTANCE The estuary of the Rio Tinto is a unique environment in which extremely acidic, heavy metal-rich, and especially iron-rich river water is mixed with seawater. Due to the mixing events, the estuarine water is characterized by a low pH, almost seawater salinity, and high concentrations of bioavailable iron. The unusual hydrogeochemistry maintains unique microbial communities in the estuarine water and in the sediment. These communities include halotolerant iron-oxidizing microorganisms which typically inhabit acidic saline environments and marine iron-oxidizing microorganisms which, in contrast, are not typically found in acidic environments. Furthermore, highly saline estuarine water favored the prosperity of acidophilic heterotrophs, typically inhabiting brackish and saline environments. The Rio Tinto estuarine sediment harbors a diverse microbial community with both acidophilic and neutrophilic members that can mediate the iron cycle and, in turn, can directly impact the mobility and transport of heavy metals in the Rio Tinto estuary.

Role of biogenic Fe(III) minerals as a sink and carrier of heavy metals in the Rio Tinto, Spain.

Oxidation of sulfide ores in the Iberian Pyrite Belt region leads to the presence of extremely high concentration of dissolved heavy metals (HMs) in the acidic water of the Rio Tinto. Fe(II) is microbially oxidized resulting in the formation of suspended particulate matter (SPM) consisting of microbial cells and Fe(III) minerals with co-precipitated HMs. Although substantial amount of HM-bearing SPM is likely deposited to river sediment, a portion can still be transported through estuary to the coastal ocean. Therefore, the mechanisms of SPM formation and transport along the Rio Tinto are important for coastal-estuarine zone. In order to reveal these mechanisms, we performed diurnal sampling of Rio Tinto water, mineralogical and elemental analysis of sediment from the middle course and the estuary of the river. We identified two divergent but interrelated pathways of HM transfer. The first longitudinal pathway is the transport of SPM-associated metals such as As (6.58 µg/L), Pb (3.51 µg/L) and Cr (1.30 µg/L) to the coastal ocean. The second sedimentation pathway contributes to the continuous burial of HMs in the sediment throughout the river. In the middle course, sediment undergoes mineralogical transformations during early diagenesis and traps HMs (e.g. 1.6 mg/g of As, 1.23 mg/g of Pb and 0.1 mg/g of Cr). In the estuary, HMs are accumulated in a distinct anoxic layer of sediment (e.g. 1.5 mg/g of As, 2.09 mg/g of Pb and 0.04 mg/g of Cr). Our results indicate that microbially precipitated Fe(III) minerals (identified as ferrihydrite and schwertmannite) play a key role in maintaining these divergent HM pathways and as a consequence are crucial for HM mobility in the Rio Tinto.

Heavy metal mobility and valuable contents of processed municipal solid waste incineration residues from Southwestern Germany.

As conventional end-of-life disposal, municipal solid waste (MSW) incineration residues can be problematic due to potential release of toxic compounds into the environment. Using municipal solid waste incineration residues as urban-mine of valuable metals (e.g. precious metals) could provide a trash-to-treasure possibility. The objectives of the study are to (i) determine the contents of different contaminant metallic elements (Zn, Cu, Ba, Pb, Cr and Ni) in four size fractions of MSW incineration residues and discuss their mobility potential by using the modified BCR sequential extraction method; (ii) investigate the level of valuable critical contents (precious metals, rare earth elements, etc.) in these wastes. We also characterized mineralogy and elemental composition of four different grain size fractions (0-0.5, 0.5-2.0, 2.0-4.0 and 4.0-16.0 mm) of processed municipal solid waste incineration residue (PIR) from the Southwestern region of Germany, using X-ray fluorescence, X-ray powder diffraction and different spectroscopic techniques. Among all studied size fractions, grains smaller than 2 mm contained higher amounts of total extractable heavy metals in most cases. The most important finding of the study is that the total contents of Cu, Au and Pt in the incineration residues reached economically profitable levels (5.1 g/kg, 21.69 mg/kg and 17.45 mg/kg, respectively).