The variability in the structural and functional properties of coccolith base plates.

Biomineralization processes exert varying levels of control over crystallization, ranging from poorly ordered polycrystalline arrays to intricately shaped single crystals. Coccoliths, calcified scales formed by unicellular algae, are a model for a highly controlled crystallization process. The coccolith crystals nucleate next to an organic oval structure that was termed the base plate, leading to the assumption that it is responsible for the oriented nucleation of the crystals via stereochemical interactions. In recent years, several works focusing on a well-characterized model species demonstrated a fundamental role for indirect interactions that facilitate coccolith crystallization. Here, we developed the tools to extract the base plates from five different species, giving the opportunity to systematically explore the relations between base plate and coccolith properties. We used multiple imaging techniques to evaluate the structural and chemical features of the base plates under native hydrated conditions. The results show a wide range of properties, overlaid on a common rudimentary scaffold that lacks any detectable structural or chemical motifs that can explain direct nucleation control. This work emphasizes that it is the combination between the base plate and the chemical environment inside the cell that cooperatively facilitate the exquisite control over the crystallization process. STATEMENT OF SIGNIFICANCE: Biological organic scaffolds can serve as functional surfaces that guide the formation of inorganic materials. However, in many cases the specific interactions that facilitate such tight regulation are complex and not fully understood. In this work, we elucidate the architecture of such amodel biological template, an organic scale that directs the assembly of exquisite crystalline arrays of marine microalgae. By using cryo electron microscopy, we reveal the native state organization of these scales from several species. The observed similarities and differences allow us to propose that the chemical microenvironment, rather than stereochemical matching, is the pivotal regulator of the process.

Plant uptake of nitrogen adsorbed to biochars made from dairy manure.

The conversion of dairy waste with high moisture contents to dry fertilizers may reduce environmental degradation while lowering crop production costs. We converted the solid portion of screw-pressed dairy manure into a sorbent for volatile ammonia (NH3) in the liquid fraction using pyrolysis and pre-treatment with carbon dioxide (CO2). The extractable N in manure biochar exposed to NH3 following CO2 pre-treatment reached 3.36 g N kg-1, 1260-fold greater extractable N than in untreated manure biochar. Ammonia exposure was 142-times more effective in increasing extractable N than immersing manure biochar in the liquid fraction containing dissolved ammonium. Radish and tomato grown in horticultural media with manure biochar treated with CO2 + NH3 promoted up to 35% greater plant growth (dry weight) and 36-83% greater N uptake compared to manure biochar alone. Uptake of N was similar between plants grown with wood biochar exposed to CO2 + NH3, compared to N-equivalent treatments. The available N in dairy waste in New York (NY) state, if pyrolyzed and treated with NH3 + CO2, is equivalent to 11,732-42,232 Mg N year-1, valued at 6-21.5 million USD year-1. Separated dairy manure treated with CO2 + NH3 can offset 23-82% of N fertilizer needs of NY State, while stabilizing both the solid and liquid fraction of manure for reduced environmental pollution.

Sequential Ammonia and Carbon Dioxide Adsorption on Pyrolyzed Biomass to Recover Waste Stream Nutrients.

The amine-rich surfaces of pyrolyzed human solid waste (py-HSW) can be "primed" or "regenerated" with carbon dioxide (CO2) to enhance their adsorption of ammonia (NH3) for use as a soil amendment. To better understand the mechanism by which CO2 exposure facilitates NH3 adsorption to py-HSW, we artificially enriched a model sorbent, pyrolyzed, oxidized wood (py-ox wood) with amine functional groups through exposure to NH3. We then exposed these N-enriched materials to CO2 and then resorbed NH3. The high heat of CO2 adsorption (Q st) on py-HSW, 49 kJ mol-1, at low surface coverage, 0.4 mmol CO2 g-1, showed that the naturally occurring N compounds in py-HSW have a high affinity for CO2. The Q st of CO2 on py-ox wood also increased after exposure to NH3, reaching 50 kJ mol-1 at 0.7 mmol CO2 g-1, demonstrating that the incorporation of N-rich functional groups by NH3 adsorption is favorable for CO2 uptake. Adsorption kinetics of py-ox wood revealed continued, albeit diminishing NH3 uptake after each CO2 treatment, averaging 5.9 mmol NH3 g-1 for the first NH3 exposure event and 3.5 and 2.9 mmol NH3 g-1 for the second and third; the electrophilic character of CO2 serves as a Lewis acid, enhancing surface affinity for NH3 uptake. Furthermore, penetration of 15NH3 and 13CO2 measured by NanoSIMS reached over 7 µm deep into both materials, explaining the large NH3 capture. We expected similar NH3 uptake in py-HSW sorbed with CO2 and py-ox wood because both materials, py-HSW and py-ox wood sorbed with NH3, had similar N contents and similarly high CO2 uptake. Yet NH3 sorption in py-HSW was unexpectedly low, apparently from potassium (K) bicarbonate precipitation, reducing interactions between NH3 and sorbed CO2; 2-fold greater surface K in py-HSW was detected after exposure to CO2 and NH3 than before gas exposure. We show that amine-rich pyrolyzed waste materials have high CO2 affinity, which facilitates NH3 uptake. However, high ash contents as found in py-HSW hinder this mechanism.

Biological and thermochemical conversion of human solid waste to soil amendments.

Biological and thermochemical sanitization of source-separated human solid waste (HSW) are effective technologies for unsewered communities. While both methods are capable of fecal pathogen sterilization, the agronomically-beneficial properties of waste sanitized between methods remains unclear. Therefore, this study compared recovery and quality of soil amendments produced by compostation, torrefaction, and pyrolysis of HSW, established their financial value, and quantified tradeoffs between product value and conversion efficiency. Temperature and associated mass losses significantly affected the physical and chemical properties of thermochemically-treated HSW. Thermophilic composting, a biological sanitation method practiced in informal settlements in Nairobi, Kenya, produced an amendment that contained between 16 and 858-fold more plant-available nitrogen (N; 214.5 mg N/kg) than HSW pyrolyzed between 300 and 700 °C (0.2-15.2 mg N/kg). Conversely, HSW pyrolyzed at 600 °C had four-fold higher plant-available phosphorus (P; 3117 mg P/kg) and five-fold higher plant-available potassium (K; 7403 mg K/kg) than composted HSW (716 mg P/kg and 1462 mg K/kg). Wide variation between international fertilizer prices on the low end and regional East African prices on the high end resulted in broad-spaced quantiles for the value of agronomic components in HSW amendments. Phosphorus and K comprised a disproportionate amount of the value, 52-87%, compared to plant-available N, which contributed less than 2%. The total value of treated HSW, summed across all agronomic components per unit weight amendment, was greatest for thermochemically-treated HSW at 600 °C, averaging 220 USD/Mg, more than four-fold that of composted HSW, 53 USD/Mg. In contrast, torrefaction provided the highest monetary value per unit weight feedstock, 144 USD/Mg, as low heating temperatures engender minimal mass loss and higher nutrient densities per unit weight feedstock, compared to composted or pyrolyzed HSW. When benchmarked against total N, P, and K of eight commonly-applied organic amendments, including sewage-sludge (Milorganite), compost, and alfalfa meal, HSW pyrolyzed at 700 °C was of greatest value per unit weight of amendment, 365 USD/Mg, compared to 89 USD/Mg for composted HSW, and contained 2.9% total N (0.5 mg available N/kg), 3.1% total P (7640 mg available P/kg), 3.5% total K (17,671 mg available K/kg).