Dawit Solomon

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy for mapping nano-scale distribution of organic carbon forms in soil: Application to black carbon particles

Received 17 December 2004; accepted 3 January 2005; published 16 February 2005. [1] Small-scale heterogeneity of organic carbon (C) forms in soils is poorly quantified since appropriate analytical techniques were not available up to now. Specifically, tools for the identification of functional groups on the surface of micrometer-sized black C particles were not available up to now. Scanning Transmission X-ray Microscopy (STXM) using synchrotron radiation was used in conjunction with Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy to investigate nano-scale distribution (50-nm resolution) of C forms in black C particles and compared to synchrotron-based FTIR spectroscopy. A new embedding technique was developed that did not build on a C-based embedding medium and did not pose the risk of heat damage to the sample. Elemental sulfur (S) was melted to 220� C until it polymerized and quenched with liquid N2 to obtain a very viscous plastic S in which the black C could be embedded until it hardened to a noncrystalline state and was ultrasectioned. Principal component and cluster analysis followed by singular value decomposition was able to resolve distinct areas in a black carbon particle. The core of the studied biomass-derived black C particles was highly aromatic even after thousands of years of exposure in soil and resembled the spectral characteristics of fresh charcoal. Surrounding this core and on the surface of the black C particle, however, much larger proportions of carboxylic and phenolic C forms were identified that were spatially and structurally distinct from the core of the particle. Cluster analysis provided evidence for both oxidation of the black C particle itself as well as adsorption of non-black C. NEXAFS spectroscopy has great potential to allow new insight into black C properties with important implications for biogeochemical cycles such as mineralization of black C in soils and sediments, and adsorption of C, nutrients, and pollutants as well as transport in the geosphere, hydrosphere, and atmosphere.

Phosphorus forms and dynamics as influenced by land use changes in the sub-humid Ethiopian highlands

Abstract In undisturbed tropical forest ecosystems, the phosphorus (P) cycle is essentially “closed” with minimal short-term losses or gains of P. The forms and dynamics of soil P, however, can be greatly affected by land use changes, which often involve changes in vegetation cover, biomass production and nutrient cycling in the ecosystem. Sequential extraction and 31 P nuclear magnetic resonance (NMR) spectroscopy were used to investigate the influence of land use changes on the amount and structural composition of P in the sub-humid highlands of southern Ethiopia. Samples were collected from surface soils (0–10 cm) of natural forest, tea plantations and cultivated fields (25 years) at Wushwush and from Podocarpus dominated natural forest, Cupressus plantations and cultivated fields (30 years) at Munesa sites. Significantly lower ( P 3 –P o ) (74% and 77%) and sodium hydroxide-extractable P o (NaOH–P o ) (67% and 67%) due to cultivation occurred in the sand, followed by the silt (52% and 56%, NaHCO 3 –P o and 32% and 53%, NaOH–P o ) and the clay (33% and 42%, NaHCO 3 –P o and 28% and 35%, NaOH–P o ) size separates from the two sites, respectively. 31 P NMR spectroscopy revealed that orthophosphate monoesters were the major organic P compounds (27–66%) followed by orthophosphate diesters (9–27%) and teichoic acids (7–11%). Unknown organic P species accounted for 3–8% (unknown A) and 3–5% (unknown B), whereas phosphonates made up 2–3%. The proportion of diester-P decreased in the order: natural forests (24% and 27%)>plantations (15% and 13%)>cultivated fields (10% and 9%) at Wushwush and Munesa, respectively. The percentages of teichoic acid, unknown A, unknown B and phosphonates also decreased, whereas the proportions of orthophosphate monoesters increased following land use changes. Greater decline in proportions of diester-P and teichoic acids were found in the silt than in the clay size separates, which may be attributed to stabilization of microbially derived organic P structures by closer association with clay minerals and/or sesquioxides. The results of sequential extraction and 31 P NMR spectroscopy indicate that continuous cultivation with little or no P input not only decreased the amount, but also influenced the structural composition and bioavailability of P in these tropical soils. Thus measures have to be designed for replenishment and subsequent maintenance of soil P stocks, to ensure sustainable crop production in sub-humid highland agroecosystems of southern Ethiopia.

Soil organic matter quantity and quality in mountain soils of the Alay Range, Kyrgyzia, affected by land use change

Abstract Changes in soil management practices influence the amount, quality and turnover of soil organic matter (SOM). Our objective was to study the effects of deforestation followed by pasture establishment on SOM quantity, quality and turnover in mountain soils of the Sui Checti valley in the Alay Range, Kyrgyzia. This objective was approached by analysis of total organic C (TOC), N, lignin-derived phenols, and neutral sugars in soil samples and primary particle-size soil fractions. Pasture installation led to a loss of about 30% TOC compared with the native Juniperus turkestanica forests. The pasture soils accumulated about 20% N, due to inputs via animal excrement. A change in land use from forest to pasture mainly affected the SOM bound to the silt fraction; there was more microbial decomposition in the pasture than in the forest silt fraction, as indicated by lower yields of lignin and carbohydrates, and also by a more advanced oxidative lignin side-chain oxidation and higher values of plant : microbial sugar ratios. The ratio of arabinose : xylose was indicative of the removal of carbohydrates when the original forest was replaced by pasture, and we conclude that this can be used as an indicator of deforestation. The accumulation of lignin and its low humification within the forest floor could be due to the extremely cold winter and dry summer climate.

Sulfur fractions in particle-size separates of the sub-humid Ethiopian highlands as influenced by land use changes

Abstract Extensive deforestation of natural forests in the Ethiopian highlands and their conversion to low-input agriculture and plantations have caused severe soil degradation and significant changes in the ecosystem. We investigated the influence of land use changes on the amount, form and distribution of sulfur (S) in bulk soils and size separates of the sub-humid highlands of southern Ethiopian. Surface soil samples (0–10 cm) were collected from natural forest, tea plantation and 25 years cultivated fields at Wushwush and from Podocarpus dominated natural forest, Cupressus plantation and 30 years cultivated fields at Munesa sites. The total S contents ranged from 635 to 1082 mg kg −1 soil and from 520 to 1040 mg kg −1 soil at Wushwush and Munesa, respectively. Organic S represented on the average 98% of the total S, while inorganic SO 4 –S accounted for only 2%. C-bonded S was the dominant organic S fraction at both sites comprising 77–84% of the total organic S pool, whereas ester SO 4 –S constituted merely for 16–23%. Total S and C-bonded S were highly significantly correlated ( P 4 –S and total S, SOC and N were weak. The C/S and N/S ratios ranged from 58 to 99 and from 5.7 to 7.9, respectively, and decreased generally in the order: sand>silt>clay. Continuous cropping resulted in 41% and 50% depletion of total S at Wushwush and Munesa, respectively. In contrast, losses from the tea (34%) and Cupressus (13%) plantations were low. Sulfur depletions due to cultivation were lower than losses from SOC (55%, Wushwush; 63%, Munesa) and N (52%, Wushwush; 60%, Munesa), suggesting that S was more resistant to mineralization compared to SOC and N. C-bonded S accounted for 88% and 73% of the total S depletion, whereas ester SO 4 –S accounted only for 11% and 26% at Wushwush and Munesa, respectively. These results indicate that most of the S depletion occurred from C-bonded S. Based on our results, it is possible to conclude that S deficiency might occur in a foreseeable future, if the current depletion rate of SOM continues. Therefore, integrated soil and crop management practices have to be developed, which involve the use of organic materials of farm and non-farm origins and inorganic fertilizers to combat the ongoing nutrient depletion in the sub-humid highlands agroecosystems of southern Ethiopia.

Land use effects on amino sugar signature of chromic Luvisol in the semi-arid part of northern Tanzania

Abstract Characterizing amino sugar signature in particle size separates of tropical soils is important for further understanding the fate of microbial-derived compounds during the decomposition of soil organic matter (SOM) in tropical agroecosystems. We investigated the impact of land-use changes on the nature, amount and dynamics of amino sugars in soil of the semi-arid northern Tanzania. Samples were collected from the uppermost 10 cm of native woodland, degraded woodland, fields cultivated for 3 and 15 years and homestead fields fertilized with animal manure. The amount of glucosamine, galactosamine, mannosamine and muramic acid were determined in bulk soil and size separates. Compared to the native woodland, a 68% and 72% reduction in total amino sugar contents were found in the 3- and 15-year cultivated fields, respectively. Moreover, 39% of the total amino sugar was lost from the degraded woodland. This may be attributed to accelerated decomposition of amino sugars and/or decreasing microbial biomass input under the semi-arid environment following clear-cutting and cultivation. In contrast, only a 20% decline was found from the fields where animal manure had been applied. Most of the amino sugar depletion occurred from the coarse and fine sand-associated SOM. The decline from the silt and clay-bound amino sugar was relatively small, indicating the importance of organo-mineral associations in the stabilization of microbial-derived sugars in this tropical soil. After 15 years of continuous cultivation, the ratio of glucosamine:galactosamine increased from 1.44 to 2.23, while the ratio of glucosamine:muramic acid increased from 14.5 to 26.5 (P<0.05). These results suggest that cultivation may have led to preferential depletion of bacterial-derived amino sugars (muramic acid and galactosamine) compared with fungal-derived glucosamine.

Effects of deforestation on phosphorus pools in mountain soils of the Alay Range, Khyrgyzia

Abstract The amount, quality and turnover of soil P is heavily influenced by changes in soil management. The objective of this study was to investigate the effects of deforestation and pasture establishment on the concentrations, forms and turnover rate of soil P in mountain soils of the Alay Range, Khyrgyzia. A sequential extraction was applied to distinguish soil P pools. We used particle-size fractionation to follow the dynamics of different P pools in soils under forest and pasture and 31P-NMR spectroscopy to investigate the structure of alkali-soluble P forms. In the A horizons of the forest soils, total soil P concentration was 1093 mg kg–1, organic P (Po) representing 46% of the total P. Deforestation followed by pasture establishment not only increased significantly (P<0.01) the total P concentration (1560 mg kg–1) but also the contribution of Po to total P was increased by 17%. Pasture soils had significantly higher P pools than forest soils except highly labile inorganic P (Pi NaHCO3) and primary Pi (Pi HCldil). Both in forest and pasture soils stable P increased with decreasing particle size (coarse sand 50%, clay 80% of total P) and primary P decreased with decreasing particle size. Phosphate monoesters and diesters represented 80% of P identified by 31P NMR. Low monoester to diester ratios in the alkali extracts of forest and pasture soils indicate low microbial activity. This is consistent with high C/Po ratios and high stable Po concentrations in the fine earth of forest and pasture.

Chapter 10 - Organic Carbon Chemistry in Soils Observed by Synchrotron-Based Spectroscopy

Abstract Synchrotron radiation opens new opportunities for the application of C (1s) near-edge X-ray absorption fine structure (NEXAFS) and Fourier transform infrared (FTIR) spectroscopy to the study of soil organic carbon chemistry. The high-energy source allows significant improvements to the signal-to-noise ratio. This is critical to analyses of soils that typically contain comparatively low amounts of C. It also offers the option for analyses at high spatial resolution including imaging of entire areas, which is key to the study of soil assemblages. Recent studies have shown that (1) soil organic matter forms are highly heterogeneous at small spatial scales; (2) the functional group chemistry of soil organic C at the submicron scale is very different from that of total soil C; (3) specific soil organic matter forms determined by FTIR relate to certain mineral forms at the spatial scale of a single aggregate; (4) organic matter filling micrometer-size pores show different functional groups than organic matter coating minerals; (5) adsorption of metal ions or protons may change spectral signatures of NEXAFS and pose both constraints and opportunities for determining interactions between minerals and C. Synchrotron-based spectroscopy has significantly contributed to recent advances in characterizing soil C chemistry. The results underpin the importance of observations at high spatial resolution for the investigation of soils that complements existing observations using other techniques. Significant advances are still needed to fully capitalize on the spectral information obtained from both FTIR and NEXAFS analyses of soils, which require detailed studies of microbial and mineral matter.

Speciation and Long- and Short-term Molecular-level Dynamics of Soil Organic Sulfur Studied by X-ray Absorption Near-Edge Structure Spectroscopy

We investigated speciation, oxidative state changes, and long- and short-term molecular-level dynamics of organic S after 365 d of aerobic incubation with and without the addition of sugarcane residue using XANES spectroscopy. Soil samples were collected from the upper 15 cm of undisturbed grasslands since 1880, from undisturbed grasslands since 1931, and from cultivated fields since 1880 in the western United States. We found three distinct groups of organosulfur compounds in these grassland-derived soils: (i) strongly reduced (S to S) organic S that encompasses thiols, monosulfides, disulfides, polysulfides, and thiophenes; (ii) organic S in intermediate oxidation (S to S) states, which include sulfoxides and sulfonates; and (iii) strongly oxidized (S) organic S, which comprises ester-SO-S. The first two groups represent S directly linked to C and accounted for 80% of the total organic S detected by XANES from the undisturbed soils. Aerobic incubation without the addition of sugarcane residue led to a 21% decline in organanosulfur compounds directly linked to C and to up to an 82% increase inorganic S directly bonded to O. Among the C-bonded S compounds, low-valence thiols, sulfides, thiophenic S, and intermediate-valence sulfoxide S seem to be highly susceptible to microbial attack and may represent the most reactive components of organic S pool in these grassland soils. Sulfonate S exhibited a much lower short-term reactivity. The incorporation of sugarcane residue resulted in an increase in organosulfur compounds directly bonded to C at the early stage of incubation. However, similar to soils incubated without residue addition, the proportion of organic S directly linked to C continued to decline with increasing duration of aerobic incubation, whereas the proportion of organic S directly bonded to O showed a steady rise.

Recycling slaughterhouse waste into fertilizer: how do pyrolysis temperature and biomass additions affect phosphorus availability and chemistry?

BACKGROUND Pyrolysis of slaughterhouse waste could promote more sustainable phosphorus (P) usage through the development of alternative P fertilizers. This study investigated how pyrolysis temperature (220, 350, 550 and 750 °C), rendering before pyrolysis, and wood or corn biomass additions affect P chemistry in bone char, plant availability, and its potential as P fertilizer. RESULTS Linear combination fitting of synchrotron-based X-ray absorption near edge structure spectra demonstrated that higher pyrolysis temperatures decreased the fit with organic P references, but increased the fit with a hydroxyapatite (HA) reference, used as an indicator of high calcium phosphate (CaP) crystallinity. The fit to the HA reference increased from 0% to 69% in bone with meat residue and from 20% to 95% in rendered bone. Biomass additions to the bone with meat residue reduced the fit to the HA reference by 83% for wood and 95% for corn, and additions to rendered bone by 37% for wood. No detectable aromatic P forms were generated by pyrolysis. High CaP crystallinity was correlated with low water-extractable P, but high formic acid-extractable P indicative of high plant availability. Bone char supplied available P which was only 24% lower than Triple Superphosphate fertilizer and two- to five-fold higher than rock phosphate. CONCLUSION Pyrolysis temperature and biomass additions can be used to design P fertilizer characteristics of bone char through changing CaP crystallinity that optimize P availability to plants.

Anthropogenic and climate influences on biogeochemical dynamics and molecular-level speciation of soil sulfur.

The soil environment is a primary component of the global biogeochemical sulfur (S) cycle, acting as a source and sink of various S species and mediating oxidation state changes. However, ecological significance of the various S forms and the impacts of human intervention and climate on the amount and structural composition of these compounds are still poorly understood. We investigated the long-term influences of anthropogenically mediated transitions from natural to managed ecosystems on molecular-level speciation, biogeochemical dynamics, and the apparent temperature sensitivity of S moieties in temperate, subtropical, and tropical environments with mean annual temperature (MAT) ranging from 5 degrees C to 21 degrees C, using elemental analysis and X-ray absorption near-edge structure (XANES) spectroscopy. Land-use and land-cover changes led to the depletion of total soil S in all three ecoregions over a period of up to 103 years. The largest decline occurred from tropical forest agroecosystems (67% Kakamega and 76% Nandi, Kenya), compared to losses from temperate (36% at Lethbridge, Canada, and 40% at Pendleton, USA) and subtropical (48% at South Africa) grassland agroecosystems. The total S losses correlated significantly with MAT. Anthropogenic interventions profoundly altered the molecular-level composition and resulted in an apparent shift in oxidation states of organic S from native ecosystems composed primarily of S moieties in intermediate and highly reduced oxidation states toward managed agroecosystems dominated by organic S rich in strongly oxidized functionalities. The most prominent change occurred in thiols and sulfides, the proportion of which decreased by 46% (Lethbridge) and 57% (Pendleton) in temperate agroecosystems, by 46% in subtropical agroecosystems, and by 79% (Nandi) and 81% (Kakamega) in tropical agroecosystems. The proportion of organic S directly linked to O increased by 81%, 168%, 40%, 92%, and 85%, respectively. Among the various organic S functionalities, thiols and sulfides seem to have higher apparent temperature sensitivity, and thus these organic S moieties may become prone to losses due to land-use changes, even from the cooler regions of the world if MAT of these regions rise in the future.