Biochar benefits carbon off-setting in blue-green infrastructure soils - A lysimeter study.

Carbon sequestration with amendments in blue-green infrastructure soils could off-set anthropogenic greenhouse gas emissions to alleviate climate change. In this 3-year study, the effects of wheat straw and its biochar on carbon sequestration in an urban landscaping soil were investigated under realistic outdoor conditions using two large-scale lysimeters. Both amendments were carried out by incorporating pellets at 0-15 cm soil depth with an equivalent initial total carbon input of 2% of the dry soil weight. Soil carbon, carbon isotope ratios, dissolved carbon in leachates, CO2-C emissions, carbon fixed in above ground vegetation, soil water content, soil bulk electrical conductivity, and water infiltration rates, were then compared between the 2 lysimeters. After 3 years, we observed that, despite having a 17.2% lower vegetation growth, soil organic and inorganic carbon content was higher by 28.8% and 41.5%, respectively, in biochar as compared to wheat straw amended soil. Carbon isotope analysis confirmed the greater stability of the added carbon in the biochar amended soil. Water content was on average 23.2% and 13.0% in the straw pellet and biochar amended soil, respectively, whereas water infiltration rates were not significantly different between the two lysimeters. Overall, the incorporation of wheat straw biochar into soil could store an estimated 30 tonnes of carbon per hectare in city blue-green infrastructure spaces. Interviews involving institution stakeholders examined the feasibility of this biochar application. Stakeholders recognized the potential of biochar as an environment-friendly means for carbon offsetting, but were concerned about the practicality of biochar production and application into soil and increased maintenance work. Consequently, additional potential benefits of biochar for environmental management such as improving the quality of polluted run-off in stormwater treatment systems should be emphasized to make biochar an attractive proposition in sustainable urban development.

Comparison of organic substrates in urban rooftop agriculture, towards improving crop production resilience to temporary drought in Mediterranean cities.

BACKGROUND: Urban agriculture contributes to meeting the growing food production demand in cities. In the context of low water availability, it is important to consider alternatives that are able to maintain production. Through a circular economy vision, this study aimed to assess the use of substrates made from local materials as an alternative for urban agriculture in periods of low water availability, due to water supply cuts. The substrates used were coir commercial organic substrate, vegetable compost from urban organic waste and perlite commercial standard substrate; a mixture of the urban compost and perlite (1:1) was used for three consecutive crop cycles of lettuce (Lactuca sativa L. var. crispa). The crop cycles were performed in the spring and summer periods of 2018 to observe the performance during warmer periods of the year in an integrated rooftop greenhouse near Barcelona. Each substrate was assessed under conventional irrigation (0-5 kPa) and temporary water restricted conditions (irrigation stopped until the water tension reached -20 kPa perlite). RESULTS: In terms of yield, our results show that the compost and mixture were similar to those obtained from perlite (11.5% and 3.7% more production under restricted water conditions). Organic substrates increased the crop's resilience to water restriction, in contrast to the perlite. In particular, water loss took longer in coir (one- and two-crop cycle); however, when dryness began, it occurred quickly. CONCLUSION: The vegetable compost and the substrate mixture presented tolerance to temporary water restriction when water restriction reached -20 kPa. © 2021 Society of Chemical Industry.

Rapid Removal of Atmospheric CO2 by Urban Soils.

The measured calcium carbonate content of soils to a depth of 100 mm at a large urban development site has increased over 18 months at a rate that corresponds to the sequestration of 85 t of CO2/ha (8.5 kg of CO2 m(-2)) annually. This is a consequence of rapid weathering of calcium silicate and hydroxide minerals derived from the demolition of concrete structures, which releases Ca that combines with CO2 ultimately derived from the atmosphere, precipitating as calcite. Stable isotope data confirm an atmospheric origin for carbonate carbon, and 14C dating indicates the predominance of modern carbon in the pedogenic calcite. Trial pits show that carbonation extends to depths of ≥1 m. Work at other sites shows that the occurrence of pedogenic carbonates is widespread in artificially created urban soils containing Ca and Mg silicate minerals. Appropriate management of fewer than 12000 ha of urban land to maximize calcite precipitation has the potential to remove 1 million t of CO2 from the atmosphere annually. The maximal global potential is estimated to be approximately 700-1200 Mt of CO2 per year (representing 2.0-3.7% of total emissions from fossil fuel combustion) based on current rates of production of industry-derived Ca- and Mg-bearing materials.

Black Carbon Contribution to Organic Carbon Stocks in Urban Soil.

Soil holds 75% of the total organic carbon (TOC) stock in terrestrial ecosystems. This comprises ecosystem-derived organic carbon (OC) and black carbon (BC), a recalcitrant product of the incomplete combustion of fossil fuels and biomass. Urban topsoils are often enriched in BC from historical emissions of soot and have high TOC concentrations, but the contribution of BC to TOC throughout the urban soil profile, at a regional scale is unknown. We sampled 55 urban soil profiles across the North East of England, a region with a history of coal burning and heavy industry. Through combined elemental and thermogravimetic analyses, we found very large total soil OC stocks (31-65 kg m(-2) to 1 m), exceeding typical values reported for UK woodland soils. BC contributed 28-39% of the TOC stocks, up to 23 kg C m(-2) to 1 m, and was affected by soil texture. The proportional contribution of the BC-rich fraction to TOC increased with soil depth, and was enriched in topsoil under trees when compared to grassland. Our findings establish the importance of urban ecosystems in storing large amounts of OC in soils and that these soils also capture a large proportion of BC particulates emitted within urban areas.

Applications of stable isotope ratio mass spectrometry in cattle dung carbon cycling studies.

Understanding the fate of dung carbon (C) in soils is challenging due to the ubiquitous presence of the plant-derived organic matter (OM), the source material from which both dung-derived OM and soil organic matter (SOM) predominantly originate. A better understanding of the fate of specific components of this substantial source of OM, and thereby its contribution to C cycling in terrestrial ecosystems, can only be achieved through the use of labelled dung treatments. In this short review, we consider analytical approaches using bulk and compound-specific stable carbon isotope analysis that have been utilised to explore the fate of dung-derived C in soils. Bulk stable carbon isotope analyses are now used routinely to explore OM matter cycling in soils, and have shown that up to 20% of applied dung C may be incorporated into the surface soil horizons several weeks after application, with up to 8% remaining in the soil profile after one year. However, whole soil delta(13)C values represent the average of a wide range of organic components with varying delta(13)C values and mean residence times in soils. Several stable (13)C isotope ratio mass spectrometric methods have been developed to qualify and quantify different fractions of OM in soils and other complex matrices. In particular, thermogravimetry-differential scanning calorimetry-isotope ratio mass spectrometry (TG-DSC-IRMS) and gas chromatography-combustion-IRMS (GC-C-IRMS) analyses have been applied to determine the incorporation and turnover of polymeric plant cell wall materials from C(4) dung into C(3) grassland soils using natural abundance (13)C isotope labelling. Both approaches showed that fluxes of C derived from polysaccharides, i.e. as cellulose or monosaccharide components, were more similar to the behaviour of bulk dung C in soil than lignin. However, lignin and its 4-hydroxypropanoid monomers were unexpectedly dynamic in soil. These findings provide further evidence for emerging themes in biogeochemical investigations of soil OM dynamics that challenge perceived concepts of recalcitrance of C pools in soils, which may have profound implications for the assessment of the potential of agricultural soils to influence terrestrial C sinks.

"Amorphous nickel sulfide" is hydrated nanocrystalline nis with a core-shell structure.

The application of a range of experimental techniques shows that "amorphous nickel sulfide" (the material precipitated from aqueous solutions of Ni(II) salts and S(II-) under ambient conditions) is actually a hydrated nanoparticulate material with an approximate formula NiS.1.5H(2)O. The particles comprise a crystalline, anhydrous core (diameter ca. 1-3 nm) with the millerite (NiS) structure, surrounded by a hydrated shell phase. The materials prepared under acidic conditions (pH = 3 and 5) transform with age to form polydymite (Ni(3)S(4)) and heazlewoodite (Ni(3)S(2)), while materials prepared at pH = 7 and 9 do not undergo this transformation. At pH = 12, the preparation procedure yields NiAs-type NiS as a metastable phase.

The organic stratigraphy of Ontong Java Plateau Tuff correlated with the depth-related presence and absence of putative microbial alteration structures.

Structures in geological samples are often interpreted as fossilised life; however, such interpretations are equivocal, as abiotic processes can be invoked to explain their presence. Thus, additional lines of chemical evidence are invaluable in confirming or refuting such morphological evidence. Glass shards in tuff from the Ontong Java Plateau (OJP) contain microtubular structures that are in close proximity to functionalised nitrogen substituted aromatic compounds that may be indicative of the chemical remnants of biological activity. The organic composition of the OJP tuff containing microtubular alteration structures was compared with tuff without such features. In addition, organic matter associated with horizons with compacted remnants of woody material buried in the OJP tuff and overlying pelagic calcareous foraminifer sediment were also characterised, to ascertain the provenance of the organic matter found in the OJP tuff. As a further control, the organic material in submarine and terrestrial basalts from other locations were also characterised providing further evidence to support the view that the organic matter in the OJP tuff is authigenic. Carbon-nitrogen chemistry was detected across all OJP tuff samples irrespective of the presence or absence of microtubular features, but was not detected in either the wood material, the overlying pelagic sediments or in the basalts from other locations. The results indicate no direct link between the OJP nitrogenous organic compounds and the presence or absence of microtubular features.

Combining thermal hydrolysis and methylation-gas chromatography/mass spectrometry with X-ray photoelectron spectroscopy to characterise complex organic assemblages in geological material.

What follows is a method applicable generically to the analysis of low levels of organic matter that is embedded in either loose fine-grained or solid geological material. Initially, the range of organic compounds that could be detected in a geological sample using conventional pyrolysis chromatography/mass spectrometry was compared to the range that was detected using thermally assisted hydrolysis and methylation-gas chromatography/mass spectrometry (THM-GC/MS). This method was used to validate the synthetic components fitted to X-ray photoelectron spectroscopy (XPS) carbon spectra of the sample. Reciprocally, XPS analysis was able to identify the constituent carbon-carbon, carbon-oxygen and carbon-nitrogen bonds of the functional groups in the compounds identified by THM-GC/MS. The two independently derived outputs from the THM-GC/MS and the XPS techniques mutually validated the identification of organic compounds in our geological samples. We describe in detail the improvements to: •The preparation of geological samples for analysis by XPS.•Measurements of organic material in geological samples using GC/MS.•The use of THM-GC/MS and XPS data used together to characterise low levels of organic material in geological samples.

Technical feasibility and carbon footprint of biochar co-production with tomato plant residue.

World tomato production is in the increase, generating large amounts of organic agricultural waste, which are currently incinerated or composted, releasing CO2 into the atmosphere. Organic waste is not only produced from conventional but also urban agricultural practices due recently gained popularity. An alternative to current waste management practices and carbon sequestration opportunity is the production of biochar (thermally converted biomass) from tomato plant residues and use as a soil amendment. To address the real contribution of biochar for greenhouse gas mitigation, it is necessary to assess the whole life cycle from the production of the tomato biomass feedstock to the actual distribution and utilisation of the biochar produced in a regional context. This study is the first step to determine the technical and environmental potential of producing biochar from tomato plant (Solanum lycopersicum arawak variety) waste biomass and utilisation as a soil amendment. The study includes the characterisation of tomato plant residue as biochar feedstock (cellulose, hemicellulose, lignin and metal content); feedstock thermal stability; and the carbon footprint of biochar production under urban agriculture at pilot and small-scale plant, and conventional agriculture at large-scale plant. Tomato plant residue is a potentially suitable biochar feedstock under current European Certification based on its lignin content (19.7%) and low metal concentration. Biomass conversion yields of over 40%, 50% carbon stabilization and low pyrolysis temperature conditions (350-400°C) would be required for biochar production to sequester carbon under urban pilot scale conditions; while large-scale biochar production from conventional agricultural practices have not the potential to sequestrate carbon because its logistics, which could be improved. Therefore, the diversion of tomato biomass waste residue from incineration or composting to biochar production for use as a soil amendment would environmentally be beneficial, but only if high biochar yields could be produced.

Characterization of the sorption of an anthranilate fungicide in soil using thermal analytical and mineralogical techniques.

The sorption of pesticides to soil particles has implications for their distribution and fate in the soil environment. A batch equilibrium technique was used to investigate sorption of the fungicide AEC623892 to intact and hydrogen-peroxide-treated whole soils and several particle-size fractions isolated from them. Sorption of AEC623892 to the soil as a whole was low. K(f oc) values measured in the whole soils were 169.2 and 41.9 ml g(-1) for Soil A and Soil B respectively. The highest values of K(f oc) were measured in soil particle-size fractions <53 microm (266.5 ml g(-1) in the 2-20 microm fraction of Soil A; 471.9 ml g(-1) in the 20-53 microm fraction of Soil B). Sorption was most irreversible in the 2-20 microm fractions. Overall, treatment of soil particle-size fractions with hydrogen peroxide resulted in lower values of K(f oc) (112.3 ml g(-1) in Soil A whole soil and 30.9 ml g(-1) in Soil B whole soil). In both soils, the maximum sorption among hydrogen-peroxide-treated samples was observed in the <2 microm fraction (166.6 and 311.0 ml g(-1) for Soil A and Soil B, respectively). Investigation of the mineralogical composition of the soils suggested that the clay mineralogy (dominated by kaolinite and illite) is less likely to account for the differences in sorption observed than differences in the characteristics of the soil organic matter. Thermal analysis of the different soil fractions indicated that hydrogen peroxide treatment preferentially removed aliphatic fractions of organic matter, but had less effect on lignin-like, aromatic fractions.

Towards a mechanistic understanding of carbon stabilization in manganese oxides.

Minerals stabilize organic carbon (OC) in sediments, thereby directly affecting global climate at multiple scales, but how they do it is far from understood. Here we show that manganese oxide (Mn oxide) in a water treatment works filter bed traps dissolved OC as coatings build up in layers around clean sand grains at 3%w/wC. Using spectroscopic and thermogravimetric methods, we identify two main OC fractions. One is thermally refractory (>550 °C) and the other is thermally more labile (<550 °C). We postulate that the thermal stability of the trapped OC is due to carboxylate groups within it bonding to Mn oxide surfaces coupled with physical entrapment within the layers. We identify a significant difference in the nature of the surface-bound OC and bulk OC . We speculate that polymerization reactions may be occurring at depth within the layers. We also propose that these processes must be considered in future studies of OC in natural systems.

Influence of recent vegetation on labile and recalcitrant carbon soil pools in central Queensland, Australia: evidence from thermal analysis-quadrupole mass spectrometry-isotope ratio mass spectrometry.

The effect of a recent vegetation change (<100 years) from C(4) grassland to C(3) woodland in central Queensland, Australia, on soil organic matter (SOM) composition and SOM dynamics has been investigated using a novel coupled thermogravimetry-differential scanning calorimetry-quadrupole.mass spectrometry-isotope ratio mass spectrometry (TG-DSC-QMS-IRMS) system. TG-DSC-QMS-IRMS distinguishes the C isotope composition of discrete SOM pools, showing changes in labile, recalcitrant and refractory carbon in the bulk soil and particle size fractions which track the vegetation changes. Analysis of evolved gases (by QMS) from thermal decomposition, rather than observed weight loss, proved essential in determining the temperature at which SOM decomposes, because smectite and kaolinite clays contribute to observed weight losses. The delta(13)C analyses of the CO(2) evolved at different temperatures for bulk soil and particle size-separates showed that most of the labile SOM under the more recent woody vegetation was C(3)-derived carbon whereas the delta(13)C values in the recalcitrant SOM showed greater C(4) contributions. This indicated a shift from grass (C(4))- to tree (C(3))-derived carbon in the woodland, which was also supported by the two-phase (13)C enrichment with depth, i.e. C(3) vegetation dominated the top soil (0-10 cm), but the C(4) contribution increased with depth (more gradual). This is perturbed by the inclusion of charcoal from forest fires ((14)C age incursions) and by the deep incorporation of C(3) carbon due to root penetration.

Carbon isotope determination for separate components of heterogeneous materials using coupled thermogravimetric analysis/isotope ratio mass spectrometry.

A gas-tight thermal analysis system (Netzsch STA 449C Jupiter) has been connected to an isotope ratio mass spectrometer (PDZ Europa 20-20) via an interface containing an oxidizing furnace, water trap, and gas-sampling valve. Using this system, delta(13)C has been measured for CO(2) derived from the thermal decomposition of carbonate and oxalate minerals and organic materials at temperatures that correspond to different decomposition events. There is close agreement between measured and published delta(13)C values for carbonate and oxalate minerals, which have simple decarbonation reactions on heating. Cellulose and lignin-rich materials show much more complex thermal decomposition, reflecting differences in their purity and structure, and measured delta(13)C values vary with the temperature of gas sampling. Provided that measurements are made at temperatures that correspond to the decomposition of cellulose and lignin (indicated by maximum weight loss), internally consistent data can be obtained. However, measurements for cellulose and lignin are systematically enriched in delta(13)C (by up to 1.4 per thousand) with respect to those reported for reference materials, possibly due to the slower combustion kinetics (compared with EA-IRMS). Thermogravimetric analysis/isotope ratio mass spectrometry (TG-IRMS) is ideal for materials and samples for which it is not possible to use other isotopic measurement techniques, for example because of sample heterogeneity.

Heterotrophic microbial communities use ancient carbon following glacial retreat.

When glaciers retreat they expose barren substrates that become colonized by organisms, beginning the process of primary succession. Recent studies reveal that heterotrophic microbial communities occur in newly exposed glacial substrates before autotrophic succession begins. This raises questions about how heterotrophic microbial communities function in the absence of carbon inputs from autotrophs. We measured patterns of soil organic matter development and changes in microbial community composition and carbon use along a 150-year chronosequence of a retreating glacier in the Austrian Alps. We found that soil microbial communities of recently deglaciated terrain differed markedly from those of later successional stages, being of lower biomass and higher abundance of bacteria relative to fungi. Moreover, we found that these initial microbial communities used ancient and recalcitrant carbon as an energy source, along with modern carbon. Only after more than 50 years of organic matter accumulation did the soil microbial community change to one supported primarily by modern carbon, most likely from recent plant production. Our findings suggest the existence of an initial stage of heterotrophic microbial community development that precedes autotrophic community assembly and is sustained, in part, by ancient carbon.