Nina Siebers

Innovative methods in soil phosphorus research: A review

Phosphorus (P) is an indispensable element for all life on Earth and, during the past decade, concerns about the future of its global supply have stimulated much research on soil P and method development. This review provides an overview of advanced state-of-the-art methods currently used in soil P research. These involve bulk and spatially resolved spectroscopic and spectrometric P speciation methods (1 and 2D NMR, IR, Raman, Q-TOF MS/MS, high resolution-MS, NanoSIMS, XRF, XPS, (µ)XAS) as well as methods for assessing soil P reactions (sorption isotherms, quantum-chemical modeling, microbial biomass P, enzymes activity, DGT, 33P isotopic exchange, 18O isotope ratios). Required experimental set-ups and the potentials and limitations of individual methods present a guide for the selection of most suitable methods or combinations.

Bone char: a clean and renewable phosphorus fertilizer with cadmium immobilization capability.

Soil contamination with Cd from P fertilizer and other anthropogenic and geogenic sources is a serious problem. In situ immobilization by P application to soil is known as an applicable remediation technique leading to reduced Cd uptake by plants, and use of a Cd-free P fertilizer from renewable sources would be most favorable. Bone char (BC) (15% P, 28% Ca, 0.7% Mg) may be used as such a quality P fertilizer, but it is unknown if its dissolution in soil provides sufficient P and immobilizes Cd in moderately contaminated soils. We incubated BC and triple superphosphate (TSP) in 11 soils that contained between 0.3 to 19.6 mg Cd kg and determined the kinetics of P dissolution during a time period of 145 d. The concomitant Cd immobilization was determined by extracting the mobile Cd with 1 mol L NHNO solution. For most soils, BC increased the concentration of labile P immediately after application, reaching a maximum after 34 d, although the solubility was below that of TSP (2.9-19.3 vs. 4.1-24.0%). Among five kinetic models, the Langmuir-type equation provided the best description of P dissolution from BC and TSP. The Cd immobilization resulting from BC dissolution exceeded that of TSP by a factor of 1.4 to 2.7. The P dissolution from BC was negatively correlated with pH and positively with P sorption capacity, whereas Cd immobilization was positively correlated with soil pH. These causal relationships were expressed in multiple equations that enable predictions of P dissolution and Cd immobilization and thus may help to introduce BC as sustainable P fertilizer and useful soil amendment.

Phosphorus Containing Water Dispersible Nanoparticles in Arable Soil

Due to the limited solubility of phosphorus (P) in soil, understanding its binding in fine colloids is vital to better forecast P dynamics and losses in agricultural systems. We hypothesized that water-dispersible P is present as nanoparticles and that iron (Fe) plays a crucial role for P binding to these nanoparticles. To test this, we isolated water-dispersible fine colloids (WDFC) from an arable topsoil (Haplic Luvisol, Germany) and assessed colloidal P forms after asymmetric flow field-flow fractionation coupled with ultraviolet and an inductively coupled plasma mass spectrometer, with and without removal of amorphous and crystalline Fe oxides using oxalate and dithionite, respectively. We found that fine colloidal P was present in two dominant sizes: (i) in associations of organic matter and amorphous Fe (Al) oxides in nanoparticles <20 nm, and (ii) in aggregates of fine clay, organic matter and Fe oxides (more crystalline Fe oxides) with a mean diameter of 170 to 225 nm. Solution P-nuclear magnetic resonance spectra indicated that the organically bound P predominantly comprised orthophosphate-monoesters. Approximately 65% of P in the WDFC was liberated after the removal of Fe oxides (especially amorphous Fe oxides). The remaining P was bound to larger-sized WDFC particles and Fe bearing phyllosilicate minerals. Intriguingly, the removal of Fe by dithionite resulted in a disaggregation of the nanoparticles, evident in higher portions of organically bound P in the <20 nm nanoparticle fraction, and a widening of size distribution pattern in larger-sized WDFC fraction. We conclude that the crystalline Fe oxides contributed to soil P sequestration by (i) acting as cementing agents contributing to soil fine colloid aggregation, and (ii) binding not only inorganic but also organic P in larger soil WDFC particles.

Recycled Products from Municipal Wastewater: Composition and Effects on Phosphorus Mobility in a Sandy Soil

Recycled products from wastewater may contain high concentrations of phosphorus (P) and are thus promising alternative fertilizers. However, to better predict their P fertilizer efficiency and potential for P leaching, investigations on P forms and P mobility in soil are essential. In this study, different recycled products-an untreated sewage sludge ash (SSA), an HSO-digested SSA, four thermochemically treated SSAs (two Mg-SSAs and two Ca-SSAs), and struvite-were investigated using a combination of wet chemical methods and P K-edge X-ray absorption near-edge structure (XANES) spectroscopy concerning their composition and their effects on P sorption in a sandy soil in comparison to triple superphosphate. Most of the P in the SSAs was associated with Ca in stable P fractions. The lowest P values in labile fractions (HO-P, NaHCO-P) were found for the untreated SSA and struvite. However, the addition of struvite resulted in an immediate increase in the bioavailable P fractions and the degree of P saturation in soil after only 1 d of incubation. This suggests a high P fertilizer potential for struvite but also a risk of P losses. Among the SSAs, the two Mg-SSAs increased the bioavailable P fractions in soil the most, whereas the lowest values were measured after application of the untreated SSA. Our results demonstrate that chemical analyses of recycled P products may involve the risk of misjudging the fertilizer quality when performed alone, without considering the behavior of these products in soil.

Role of rain intensity and soil colloids in the retention of surfactant-stabilized silver nanoparticles in soil

Undisturbed outdoor lysimeters containing arable loamy sand soil were used to examine the influence of either heavy rain events (high frequency of high rain intensity), steady rain (continuous rainfall of low rain intensity), and natural rainfall on the transport and retention of surfactant-stabilized silver nanoparticles (AgNP). In addition, the AgNP-soil associations within the Ap horizon were analyzed by means of particle-size fractionation, asymmetrical flow field-flow fractionation coupled with UV/Vis-detection and inductively coupled plasma mass spectrometer (AF4-UV/Vis-ICP-MS), and transmission electron microscopy coupled to an energy-dispersive X-ray (TEM-EDX) analyzer. The results showed that AgNP breakthrough for all rain events was less than 0.1% of the total AgNP mass applied, highlighting that nearly all AgNP were retained in the soil. Heavy rain treatment and natural rainfall revealed enhanced AgNP transport within the Ap horizon, which was attributed to the high pore water flow velocities and to the mobilization of AgNP-soil colloid associations. Particle-size fractionation of the soil revealed that AgNP were present in each size fraction and therefore indicated strong associations between AgNP and soil. In particular, water-dispersible colloids (WDC) in the size range of 0.45-0.1 μm were found to exhibit high potential for AgNP attachment. The AF4-UV/Vis-ICP-MS and TEM-EDX analyses of the WDC fraction confirmed that AgNP were persistent in soil and associated to soil colloids (mainly composed of Al, Fe, Si, and organic matter). These results confirm the particularly important role of soil colloids in the retention and remobilization of AgNP in soil. Furthermore, AF4-UV/Vis-ICP-MS results indicated the presence of single, homo-aggregated, and small AgNP probably due to dissolution.