Corrigendum to "An open-source, automated, gas sampling peripheral for laboratory incubation experiments using cavity ring-down spectroscopy" [HardwareX 10 (2021) e00208].

[This corrects the article DOI: 10.1016/j.ohx.2021.e00208.].

Suppressing peatland methane production by electron snorkeling through pyrogenic carbon in controlled laboratory incubations.

Northern peatlands are experiencing more frequent and severe fire events as a result of changing climate conditions. Recent studies show that such a fire-regime change imposes a direct climate-warming impact by emitting large amounts of carbon into the atmosphere. However, the fires also convert parts of the burnt biomass into pyrogenic carbon. Here, we show a potential climate-cooling impact induced by fire-derived pyrogenic carbon in laboratory incubations. We found that the accumulation of pyrogenic carbon reduced post-fire methane production from warm (32 °C) incubated peatland soils by 13-24%. The redox-cycling, capacitive, and conductive electron transfer mechanisms in pyrogenic carbon functioned as an electron snorkel, which facilitated extracellular electron transfer and stimulated soil alternative microbial respiration to suppress methane production. Our results highlight an important, but overlooked, function of pyrogenic carbon in neutralizing forest fire emissions and call for its consideration in the global carbon budget estimation.

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.

Microbial community shifts reflect losses of native soil carbon with pyrogenic and fresh organic matter additions and are greatest in low-carbon soils.

Soil organic carbon (SOC) plays an important role in regulating global climate change, carbon and nutrient cycling in soils, and soil moisture. Organic matter (OM) additions to soils can affect the rate at which SOC is mineralized by microbes, with potentially important effects on SOC stocks. Understanding how pyrogenic organic matter (PyOM) affects the cycling of native SOC (nSOC) and the soil microbes responsible for these effects is important for fire-affected ecosystems as well as for biochar-amended systems. We used an incubation trial with five different soils from National Ecological Observatory Network sites across the US and 13C-labelled 350°C corn stover PyOM and fresh corn stover OM to trace nSOC-derived CO2 emissions with and without PyOM and OM amendments. We used high-throughput sequencing of rRNA genes to characterize bacterial, archaeal, and fungal communities and their response to PyOM and OM in soils that were previously stored at -80°C. We found that the effects of amendments on nSOC-derived CO2 reflected the unamended soil C status, where relative increases in C mineralization were greatest in low-C soils. OM additions produced much greater effects on nSOC-CO2 emissions than PyOM additions. Furthermore, the magnitude of microbial community composition change mirrored the magnitude of increases in nSOC-CO2, indicating a specific subset of microbes were likely responsible for the observed changes in nSOC mineralization. However, PyOM responders differed across soils and did not necessarily reflect a common "charosphere". Overall, this study suggests that soils that already have low SOC may be particularly vulnerable to short-term increases in SOC loss with OM or PyOM additions.Importance Soil organic matter (SOM) has an important role in global climate change, carbon and nutrient cycling in soils, and soil moisture dynamics. Understanding the processes that affect SOM stocks is important for managing these functions. Recently, understanding how fire-affected organic matter (or "pyrogenic" organic matter (PyOM)) affects existing SOM stocks has become increasingly important, both due to changing fire regimes, and to interest in "biochar" - pyrogenic organic matter that is produced intentionally for carbon management or as an agricultural soil amendment. We found that soils with less SOM were more prone to increased losses with PyOM (and fresh organic matter) additions, and that soil microbial communities changed more in soils that also had greater SOM losses with PyOM additions. This suggests that soils that already have low SOM content may be particularly vulnerable to short-term increases in SOM loss, and that a subset of the soil microbial community is likely responsible for these effects.

An open-source, automated, gas sampling peripheral for laboratory incubation experiments using cavity ring-down spectroscopy.

Spectroscopic instruments are becoming increasingly popular for measuring the isotopic composition and fluxes of a wide variety of gases in both field and laboratory experiments. The popularity of these instruments has created a need for automated multiplexers compatible with the equipment. While there are several such peripherals commercially available, they are currently limited to only a small number of samples (≤16), which is insufficient for some studies. To support researchers in constructing custom, larger-scale systems, we present our design for a scalable gas sampling peripheral that can be programmed to autonomously sample up to 56 vessels - the "multiplexer". While originally designed to be used with a Picarro cavity ring-down spectroscopy (CRDS) system, the multiplexer design and data processing approach implemented can be easily adapted to serve as a gas sampling/delivery platform for a wide variety of instruments including other cavity ring-down systems and infra-red gas analyzers. We demonstrate the basic capabilities of the multiplexer by using it to autonomously sample head-space CO2 from 14 laboratory-incubated soils amended with 13C-enriched pyrogenic organic matter for analysis in a Picarro G2201-i cavity ring-down spectroscopy system.

Organo-organic and organo-mineral interfaces in soil at the nanometer scale.

The capacity of soil as a carbon (C) sink is mediated by interactions between organic matter and mineral phases. However, previously proposed layered accumulation of organic matter within aggregate organo-mineral microstructures has not yet been confirmed by direct visualization at the necessary nanometer-scale spatial resolution. Here, we identify disordered micrometer-size organic phases rather than previously reported ordered gradients in C functional groups. Using cryo-electron microscopy with electron energy loss spectroscopy (EELS), we show organo-organic interfaces in contrast to exclusively organo-mineral interfaces. Single-digit nanometer-size layers of C forms were detected at the organo-organic interface, showing alkyl C and nitrogen (N) enrichment (by 4 and 7%, respectively). At the organo-mineral interface, 88% (72-92%) and 33% (16-53%) enrichment of N and oxidized C, respectively, indicate different stabilization processes than at organo-organic interfaces. However, N enrichment at both interface types points towards the importance of N-rich residues for greater C sequestration.

Ammonia volatilization from composting with oxidized biochar.

Animal manure, agricultural residues, and other sources of biomass can be diverted from the waste stream and composted into valuable fertilizer. However, composting often results in substantial N loss through NH3 gas volatilization. We investigated biochar's capacity to improve NH3 -N retention during composting of poultry manure and straw. After 7 wk, total N loss from composting with unoxidized biochar was twofold and sixfold higher than N loss from composting with oxidized biochar and without biochar (307, 142, and 51 mg N g-1 N in the initial compost feedstocks, respectively). When cumulative NH3 -N loss was calculated relative to CO2 -C loss to account for differences in microbial activity, NH3 -N/CO2 -C loss from compost with oxidized biochar was 55% lower than from compost with unoxidized biochar (82% lower based on mass balance). Oxidized biochar particles removed from compost after 7 wk retained 16.0 mg N g-1 biochar, compared with only 6.1 mg N g-1 retained by unoxidized biochar, suggesting that N retention by biochar particles provides a mechanism for reduced NH3 -N loss. These data show that oxidized biochar enhanced microbial activity, doubled composting rate, and reduced NH3 -N loss compared with unoxidized biochar and that biochar's physiochemical characteristics modulate its performance in compost. In particular, the presence of oxidized surface functional groups, which can be increased artificially or through environmental weathering, appear to play an important role in key compost processes. This has implications for other natural and managed systems where pyrogenic organic matter may mediate biological activity and nutrient cycles.

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).

Simultaneous Quantification of Electron Transfer by Carbon Matrices and Functional Groups in Pyrogenic Carbon.

Pyrogenic carbon contains redox-active functional groups and polyaromatic carbon matrices that are both capable of transferring electrons. Several techniques have been explored to characterize the individual electron transfer process of either functional groups or carbon matrices individually. However, simultaneous analysis of both processes remains challenging. Using an approach that employs a four-electrode configuration and dual-interface electron transfer detection, we distinguished the electron transfer by functional groups from the electron transfer by carbon matrices and simultaneously quantified their relative contribution to the total electron transfer to and from pyrogenic carbon. Results show that at low to intermediate pyrolysis temperatures (400-500 °C), redox cycling of functional groups is the major mechanism with a contribution of 100-78% to the total electron transfer; whereas at high temperatures (650-800 °C), direct electron transfer of carbon matrices dominates electron transfer with a contribution of 87-100%. Spectroscopic and diffraction analyses of pyrogenic carbon support the electrochemical measurements by showing a molecular-level structural transition from an enrichment in functional groups to an enrichment in nanosized graphene domains with increasing pyrolysis temperatures. The method described in this study provides a new analytical approach to separately quantify the relative importance of different electron transfer pathways in natural pyrogenic carbon and has potential applications for engineered carbon materials such as graphene oxides.

Rapid electron transfer by the carbon matrix in natural pyrogenic carbon.

Surface functional groups constitute major electroactive components in pyrogenic carbon. However, the electrochemical properties of pyrogenic carbon matrices and the kinetic preference of functional groups or carbon matrices for electron transfer remain unknown. Here we show that environmentally relevant pyrogenic carbon with average H/C and O/C ratios of less than 0.35 and 0.09 can directly transfer electrons more than three times faster than the charging and discharging cycles of surface functional groups and have a 1.5 V potential range for biogeochemical reactions that invoke electron transfer processes. Surface functional groups contribute to the overall electron flux of pyrogenic carbon to a lesser extent with greater pyrolysis temperature due to lower charging and discharging capacities, although the charging and discharging kinetics remain unchanged. This study could spur the development of a new generation of biogeochemical electron flux models that focus on the bacteria-carbon-mineral conductive network.

Dynamics of microbial community composition and soil organic carbon mineralization in soil following addition of pyrogenic and fresh organic matter.

Pyrogenic organic matter (PyOM) additions to soils can have large impacts on soil organic carbon (SOC) cycling. As the soil microbial community drives SOC fluxes, understanding how PyOM additions affect soil microbes is essential to understanding how PyOM affects SOC. We studied SOC dynamics and surveyed soil bacterial communities after OM additions in a field experiment. We produced and mixed in either 350 °C corn stover PyOM or an equivalent initial amount of dried corn stover to a Typic Fragiudept soil. Stover increased SOC-derived and total CO2 fluxes (up to 6x), and caused rapid and persistent changes in bacterial community composition over 82 days. In contrast, PyOM only temporarily increased total soil CO2 fluxes (up to 2x) and caused fewer changes in bacterial community composition. Of the operational taxonomic units (OTUs) that increased in response to PyOM additions, 70% also responded to stover additions. These OTUs likely thrive on easily mineralizable carbon (C) that is found both in stover and, to a lesser extent, in PyOM. In contrast, we also identified unique PyOM responders, which may respond to substrates such as polyaromatic C. In particular, members of Gemmatimonadetes tended to increase in relative abundance in response to PyOM but not to fresh organic matter. We identify taxa to target for future investigations of the mechanistic underpinnings of ecological phenomena associated with PyOM additions to soil.

Toward the Standardization of Biochar Analysis: The COST Action TD1107 Interlaboratory Comparison.

Biochar produced by pyrolysis of organic residues is increasingly used for soil amendment and many other applications. However, analytical methods for its physical and chemical characterization are yet far from being specifically adapted, optimized, and standardized. Therefore, COST Action TD1107 conducted an interlaboratory comparison in which 22 laboratories from 12 countries analyzed three different types of biochar for 38 physical-chemical parameters (macro- and microelements, heavy metals, polycyclic aromatic hydrocarbons, pH, electrical conductivity, and specific surface area) with their preferential methods. The data were evaluated in detail using professional interlaboratory testing software. Whereas intralaboratory repeatability was generally good or at least acceptable, interlaboratory reproducibility was mostly not (20% < mean reproducibility standard deviation < 460%). This paper contributes to better comparability of biochar data published already and provides recommendations to improve and harmonize specific methods for biochar analysis in the future.

Adsorption and desorption of ammonium by maple wood biochar as a function of oxidation and pH.

The objective of this work was to investigate the retention mechanisms of ammonium in aqueous solution by using progressively oxidized maple wood biochar at different pH values. Hydrogen peroxide was used to oxidize the biochar to pH values ranging from 8.1 to 3.7, with one set being adjusted to a pH of 7 afterwards. Oxidizing the biochars at their lowered pH did not increase their ability to adsorb ammonium. However, neutralizing the oxygen-containing surface functional groups on oxidized biochar to pH 7 increased ammonia adsorption two to three-fold for biochars originally at pH 3.7-6, but did not change adsorption of biochars oxidized to pH 7 and above. The adsorption characteristics of ammonium are well described by the Freundlich equation. Adsorption was not fully reversible in water, and less than 27% ammonium was desorbed in water in two consecutive steps than previously adsorbed, for biochars with a pH below 7, irrespective of oxidation. Recovery using an extraction with 2M KCl increased from 34% to 99% of ammonium undesorbed by both preceding water extractions with increasing oxidation, largely irrespective of pH adjustment. Unrecovered ammonium in all extractions and residual biochar was negligible at high oxidation, but increased to 39% of initially adsorbed amounts at high pH, likely due to low amounts adsorbed and possible ammonia volatilization losses.

Trace element biogeochemistry in the soil-water-plant system of a temperate agricultural soil amended with different biochars.

Various biochar (BC) types have been investigated as soil amendment; however, information on their effects on trace element (TE) biogeochemistry in the soil-water-plant system is still scarce. In the present study, we determined aqua-regia (AR) and water-extractable TEs of four BC types (woodchips (WC), wheat straw (WS), vineyard pruning (VP), pyrolyzed at 525 °C, of which VP was also pyrolyzed at 400 °C) and studied their effects on TE concentrations in leachates and mustard (Sinapis alba L.) tissue in a greenhouse pot experiment. We used an acidic, sandy agricultural soil and a BC application rate of 3% (w/w). Our results show that contents and extractability of TEs in the BCs and effectuated changes of TE biogeochemistry in the soil-water-plant system strongly varied among the different BC types. High AR-digestable Cu was found in VP and high B contents in WC. WS had the highest impact on TEs in leachates showing increased concentrations of As, Cd, Mo, and Se, whereas WC application resulted in enhanced leaching of B. All BC types increased Mo and decreased Cu concentrations in the plant tissue; however, they showed diverging effects on Cu in the leachates with decreased concentrations for WC and WS, but increased concentrations for both VPs. Our results demonstrate that BCs may release TEs into the soil-water-plant system. A BC-induced liming effect in acidic soils may lead to decreased plant uptake of cationic TEs, including Pb and Cd, but may enhance the mobility of anionic TEs like Mo and As. We also found that BCs with high salt contents (e.g., straw-based BCs) may lead to increased mobility of both anionic and cationic TEs in the short term.

Biochar and denitrification in soils: when, how much and why does biochar reduce N2O emissions?

Agricultural soils represent the main source of anthropogenic N2O emissions. Recently, interactions of black carbon with the nitrogen cycle have been recognized and the use of biochar is being investigated as a means to reduce N2O emissions. However, the mechanisms of reduction remain unclear. Here we demonstrate the significant impact of biochar on denitrification, with a consistent decrease in N2O emissions by 10-90% in 14 different agricultural soils. Using the (15)N gas-flux method we observed a consistent reduction of the N2O/(N2 + N2O) ratio, which demonstrates that biochar facilitates the last step of denitrification. Biochar acid buffer capacity was identified as an important aspect for mitigation that was not primarily caused by a pH shift in soil. We propose the function of biochar as an "electron shuttle" that facilitates the transfer of electrons to soil denitrifying microorganisms, which together with its liming effect would promote the reduction of N2O to N2.

Characterization of biochars to evaluate recalcitrance and agronomic performance.

Biochars (n=94) were found to have ash contents from 0.4% to 88.2%, volatile matter from 13.2% to 70.0%, and fixed carbon from 0% to 77.4% (w/w). Greater pyrolysis temperature for low-ash biochars increased fixed carbon, but decreased it for biochars with more than 20% ash. Nitrogen recovery varied depending on feedstock used to a greater extent (12-68%) than organic (25-45%) or total C (41-76%) at a pyrolysis temperature of 600 °C. Fixed carbon production ranged from no enrichment in poultry biochar to a 10-fold increase in corn biochar (at 600 °C). Prediction of biochar stability was improved by a combination of volatile matter and H:C ratios corrected for inorganic C. In contrast to stability, agronomic utility of biochars is not an absolute value, as it needs to meet local soil constraints. Woody feedstock demonstrated the greatest versatility with pH values ranging from 4 to 9.