Does climate-smart agriculture improve household income and food security? Evidence from Southern Ethiopia.

Climate change threatens African countries' economic development and affects agriculture and food security. Ethiopia is especially vulnerable to the negative effects of climate change because its economy is dependent on climate-sensitive livelihoods that have limited potential for adaptation. Emerging evidence indicates that climate-smart agriculture (CSA) can help smallholder farmers adapt to climate change and increase agricultural productivity, thereby enhancing household income and food security. In the study area, different CSA practices have been adopted to mitigate the negative effects of climate change and improve agricultural productivity, income, and food security. Therefore, this study examines the impact of CSA practices on household income and food security in southern Ethiopia. A total of 385 households were selected using multistage sampling. Primary and secondary data were used, and propensity score matching with different types of matching algorithms, such as nearest neighbor, kernel, and radius matching, was employed to quantify the conditional impacts of CSA intervention on farm income and food security. In comparison with non adopters farmers that have adopted CSA practices had a higher food consumption score between 6.27 and 8.15, which was statistically significant at the 1% level. Overall, 34.55% of interviewed households had acceptable food consumption scores, 44.68% had borderline, and 20.77% had poor food consumption scores. Furthermore, households that adopted CSA practices had a 20.30% higher average annual farm income per hectare than non-adopters. The study suggests that effective extension services, accurate climate information, and sound policy support are required to promote and scale up CSA measures in the study area to improve farmers' adaptive capacity, farm income, and food security.

Impacts of intensifying or expanding cereal cropping in sub-Saharan Africa on greenhouse gas emissions and food security.

Cropping is responsible for substantial emissions of greenhouse gasses (GHGs) worldwide through the use of fertilizers and through expansion of agricultural land and associated carbon losses. Especially in sub-Saharan Africa (SSA), GHG emissions from these processes might increase steeply in coming decades, due to tripling demand for food until 2050 to match the steep population growth. This study assesses the impact of achieving cereal self-sufficiency by the year 2050 for 10 SSA countries on GHG emissions related to different scenarios of increasing cereal production, ranging from intensifying production to agricultural area expansion. We also assessed different nutrient management variants in the intensification. Our analysis revealed that irrespective of intensification or extensification, GHG emissions of the 10 countries jointly are at least 50% higher in 2050 than in 2015. Intensification will come, depending on the nutrient use efficiency achieved, with large increases in nutrient inputs and associated GHG emissions. However, matching food demand through conversion of forest and grasslands to cereal area likely results in much higher GHG emissions. Moreover, many countries lack enough suitable land for cereal expansion to match food demand. In addition, we analysed the uncertainty in our GHG estimates and found that it is caused primarily by uncertainty in the IPCC Tier 1 coefficient for direct N2 O emissions, and by the agronomic nitrogen use efficiency (N-AE). In conclusion, intensification scenarios are clearly superior to expansion scenarios in terms of climate change mitigation, but only if current N-AE is increased to levels commonly achieved in, for example, the United States, and which have been demonstrated to be feasible in some locations in SSA. As such, intensifying cereal production with good agronomy and nutrient management is essential to moderate inevitable increases in GHG emissions. Sustainably increasing crop production in SSA is therefore a daunting challenge in the coming decades.

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.

Going to scale-From community-based to population-wide genetic improvement and commercialized sheep meat supply in Ethiopia.

Community-based breeding programs (CBBPs) have shown, at pilot scale, to be effective and beneficial in achieving genetic progress and in improving livelihoods of smallholder communities. In Ethiopia 134 sheep and goat CBBPs were operational producing their own improved rams and bucks. Based on experience the implementation of further programs is possible with appropriate private and public support. A different challenge is the efficient dissemination of the improved genetics produced in current CBBPs to create population-wide economic impact. We present a framework applied to the Ethiopian Washera sheep breed to meet this challenge. We propose the establishment of a genetic improvement structure that supports a meat commercialization model based on the integration of community-based breeding program cooperatives, client communities and complementary services such as fattening enterprises. We calculated that the recently established 28 community-based breeding programs in the Washera breeding tract can provide genetically improved rams to 22% of the four million head. To reach the whole population 152 additional CBBPs are needed. We simulated the genetic improvements obtainable in the current 28 CBBPs assuming realized genetic progress in CBBPs of a similar breed and calculated the expected additional lamb carcass meat production after 10 years of selection to be 7 tons and the accumulated discounted benefit 327 thousand USD. These benefits could be increased if the CBBPs are linked to client communities by providing them with improved rams: additional meat production would be 138 tons with a value of 3,088 thousand USD. The total meat production of the existing Washera CBBPs was calculated at 152 tons and the joint meat production of CBBPs if integrated with client communities would be 3,495 tons. A full integration model, which includes enterprises purchasing lambs for fattening, can produce up to 4,255 tons of meat. We conclude that Washera CBBPs cooperatives can benefit from a higher level of organization to produce population-wide genetic improvement and economic benefits. Unlike in the dairy and chicken industries, for low input sheep and goat smallholder systems the proposed commercialization model puts breeder cooperatives at the center of the operation. Cooperatives need to be capacitated and supported to become fully functional business ventures.

How to succeed in implementing community-based breeding programs: Lessons from the field in Eastern and Southern Africa.

Breeding programs involving either centralized nucleus schemes and/or importation of exotic germplasm for crossbreeding were not successful and sustainable in most Africa countries. Community-based breeding programs (CBBPs) are now suggested as alternatives that aim to improve local breeds and concurrently conserve them. Community-based breeding program is unique in that it involves the different actors from the initial phase of design up until implementation of the programs, gives farmers the knowledge, skills and support they need to continue making improvements long into the future and is suitable for low input systems. In Ethiopia, we piloted CBBPs in sheep and goats, and the results show that they are technically feasible to implement, generate genetic gains in breeding goal traits and result in socio-economic impact. In Malawi, CBBPs were piloted in local goats, and results showed substantial gain in production traits of growth and carcass yields. CBBPs are currently being integrated into goat pass-on programs in few NGOs and is out-scaled to local pig production. Impressive results have also been generated from pilot CBBPs in Tanzania. From experiential monitoring and learning, their success depends on the following: 1) identification of the right beneficiaries; 2) clear framework for dissemination of improved genetics and an up/out scaling strategy; 3) institutional arrangements including establishment of breeders' cooperatives to support functionality and sustainability; 4) capacity development of the different actors on animal husbandry, breeding practices, breeding value estimation and sound financial management; 5) easy to use mobile applications for data collection and management; 6) long-term technical support mainly in data management, analysis and feedback of estimated breeding values from committed and accessible technical staff; 7) complementary services including disease prevention and control, proper feeding, and market linkages for improved genotypes and non-selected counterparts; 8) a system for certification of breeding rams/bucks to ensure quality control; 9) periodic program evaluation and impact assessment; and 10) flexibility in the implementation of the programs. Lessons relating to technical, institutional, community dynamics and the innovative approaches followed are discussed.

Knowledge of climate change and adaptation by smallholder farmers: evidence from southern Ethiopia.

Climate change has the greatest negative impact on low-income countries, which burdens agricultural systems. Climate change and extreme weather events have caused Ethiopia's agricultural production to decline and exacerbated food insecurity over the last few decades. This study investigates whether farmers' awareness and perceptions of climate change play a role in climate change adaptation using climate-smart agricultural practices. To collect data, 385 households in Southern Ethiopia were sampled using a multistage sampling. A Heckman probit two-stage selection model was applied to investigate the factors influencing farmers' perceptions to climate change and adaptation measures through adoption of climate-smart agriculture practices, complemented with key informant interviews and focused group discussions. The results indicated that most farmers (81.80%) perceived that the local climate is changing, with 71.9% reporting increased temperature and 53.15% reporting decreasing rainfall distribution. Therefore, farmers attempted to apply some adaptation practices, including soil and water conservation with biological measures, improved crop varieties, agroforestry, improved breeds, cut and carry system, controlled grazing, and residue incorporation. The empirical results revealed that farmers adaptation to climate change through adoptions of CSA practices was significantly influenced by education, family size, gender, landholding size, farming experience, access to climate information, training received, social membership, livestock ownership, farm income and extension services. The study found that farmers' perceptions of climate change and variability were significantly influenced by their age, level of education, farming experience, and access to climate information, hence, the need to focus on enhancing the accuracy of weather information, strengthening extension services, and considering a gender-sensitive adaptation approach toward improving farmers' knowledge and aspirations. Agricultural policies should support the efforts of farmers to increase the reliance on climate risk and alleviate farmers' difficulties in adopting climate-smart agriculture practices.

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.

Model comparison and quantification of nitrous oxide emission and mitigation potential from maize and wheat fields at a global scale.

Maize and wheat are major cereals that contribute two-thirds of the food energy intake globally. The two crops consume about 35% of the nitrogen (N) fertilizer used in agriculture and thereby contribute to fertilizer-induced nitrous oxide (N2O) emissions. Thus, estimation of spatially disaggregated N2O emissions from maize and wheat fields on a global scale could be useful for identifying emission and mitigation hotspots. It could also be needed for prioritizing mitigation options consistent with location-specific production and environmental goals. N2O emission from four models (CCAFS-MOT, IPCC Tier-I, IPCC Tier-II and Tropical N2O) using a standard gridded dataset from global maize and wheat fields were compared and their performance evaluated using measured N2O emission data points (777 globally distributed datapoints). The models were used to quantify spatially disaggregated N2O emission and mitigation potential from maize and wheat fields globally and the values were compared. Although the models differed in their performance of capturing the level of measured N2O emissions, they produced similar spatial patterns of annual N2O emissions from maize and wheat fields. Irrespective of the models, predicted N2O emissions per hectare were higher in some countries in East and South Asia, North America, and Western Europe, driven mainly by higher N application rates. The study indicated a substantial N2O abatement potential if application of excess N in the maize and wheat systems is reduced without compromising the yield of the crops through technological and crop management innovations. N2O mitigation potential is higher in those countries and regions where N application rates and current N2O emissions are already high. The estimated mitigation potentials are useful for hotspot countries to target fertilizer and crop management as one of the mitigation options in their Nationally Determined Contributions (NDCs) to the United Nations Framework Convention on Climate Change (UNFCCC).

Global high-resolution gridded dataset of N2O Emission and mitigation potential from maize and wheat fields.

This data article provides a high-resolution raw data on Nitrous Oxide (N2O) emission and its mitigation potential from global maize and wheat fields. The analytical results, discussion and conclusion thereof is presented in the related manuscript "Model Comparison and Quantification of Nitrous Oxide Emission and Mitigation Potential from Maize and Wheat Fields at a Global Scale" [1]. This raw dataset has a spatial resolution of 0.0833° × 0.0833°, and comprises pixel level baseline emissions estimated using four empirical N2O emission models (CCAFS-MOT, IPCC Tier-I, IPCC Tier-II and Tropical-N2O) and the model results were validated using experimental data extracted from the literature. Spatially explicit soil, climate and crop management data were obtained from various sources detailed in "Experimental Design, Materials and Methods" section below. N2O mitigation potential were then quantified under four scenarios of excess nitrogen reduction (i.e. 25%, 50%, 75% and 100% reduction of excess nitrogen). We believe that the dataset is a valuable source of information to assess N2O emissions and mitigation measures from maize and wheat fields and to make informed decision. Countries can use this dataset to determine emissions reduction targets in their nationally determined contributions (NDCs) from agricultural sector.

Evaluation of acute and sub-acute toxicity of selected traditional antiurolithiatic medicinal plant extracts in Wistar albino rats.

INTRODUCTION: Achyranthes aspera, Chenopodium murale, Satureja punctata, Rumex abyssinicus and Aloe pulcherrima are traditionally used to treat urolithiasis in Ethiopia. However, there are limited reports on toxicity studies. OBJECTIVE: This study was intended to evaluate the acute and sub-acute toxicity effects of plants. MATERIALS AND METHODS: The crude extracts of A. aspera and C. murale leaves, S. punctata aerial parts, R. abyssinicus rhizomes, and A. Pulcherrima gel were prepared using 70 % ethanol. In acute toxicity, 125, 500 and 2000 mg/kg were tested in a stepwise manner; whereas 2000 mg/kg administrated to female rats using gavage during sub-acute toxicity. On day 14 and 28, blood samples were collected from retro-orbital sinus; liver and kidneys of each animal were collected under anaesthesia. Data were analyzed using one-way ANOVA, Dunnett's comparison test of the Graph Pad Prism. RESULTS: No mortality and significant weight loss for all extracts in both toxicity tests. In acute toxicity, C. murale extract significantly reduced hemoglobin and platelets (P < 0.01) compared with the control. Likewise, S. punctata (P < 0.05) and R. abyssinicus (P < 0.01) extracts revealed significant reduction in platelet count. An exposure to C. murale and R. abyssinicus extracts reduced the concentrations of platelet distribution width and platelet larger cell ratio (p < 0.05) during sub-acute toxicity test. The level of creatinine reduced due to A. aspera extract administrations(P < 0.05). Liver histopathological examinations revealed focal periportal hepatitis following sub-acute toxicity test of C. murale. Histopathological studies of liver demonstrated that R. abyssinicus, A. aspera and S. punctata extracts showed mild acute liver injury. A. pulcherrima was not associated with any toxicity. CONCLUSION: C. murale extract showed hematological, and histopathological toxicity profiles in rats. Furthermore, chronic toxicity studies of A. aspera, S. punctata and R. abyssinicus extracts would be beneficial to ensure safety.

Nitrogen speciation and transformations in fire-derived organic matter.

Vegetation fires are known to have broad geochemical effects on carbon (C) cycles in the Earth system, yet limited information is available for nitrogen (N). In this study, we evaluated how charring organic matter (OM) to pyrogenic OM (PyOM) altered the N molecular structure and affected subsequent C and N mineralization. Nitrogen near-edge X-ray absorption fine structure (NEXAFS) of uncharred OM, PyOM, PyOM toluene extract, and PyOM after toluene extraction were used to predict PyOM-C and -N mineralization potentials. PyOM was produced from three different plants (e.g. Maize-Zea mays L.; Ryegrass-Lollium perenne L.; and Willow-Salix viminalix L.) each with varying initial N contents at three pyrolysis temperatures (350, 500 and 700 °C). Mineralization of C and N was measured from incubations of uncharred OM and PyOM in a sand matrix for 256 days at 30 °C. As pyrolysis temperature increased from 350 to 700 °C, aromatic C[bond, double bond]N in 6-membered rings (putative) increased threefold. Aromatic C[bond, double bond]N in 6-membered oxygenated ring increased sevenfold, and quaternary aromatic N doubled. Initial uncharred OM-N content was positively correlated with the proportion of heterocyclic aromatic N in PyOM (R2 = 0.44; P < 0.0001; n = 42). A 55% increase of aromatic N heterocycles at high OM-N content, when compared to low OM-N content, suggests that higher concentrations of N favor the incorporation of N atoms into aromatic structures by overcoming the energy barrier associated with the electronic and atomic configuration of the C structure. A ten-fold increase of aromatic C[bond, double bond]N in 6-membered rings (putative) in PyOM (as proportion of all PyOM-N) decreased C mineralization by 87%, whereas total N contents and C:N ratios of PyOM had no effects on C mineralization of PyOM-C for both pyrolysis temperatures (for PyOM-350 °C, R2 = 0.15; P < 0.27; for PyOM-700 °C, R2 = 0.22; P < 0.21). Oxidized aromatic N in PyOM toluene extracts correlated with higher C mineralization, whereas aromatic N in 6-membered heterocycles correlated with reduced C mineralization (R2 = 0.56; P = 0.001; n = 100). Similarly, aromatic N in 6-membered heterocycles in PyOM remaining after toluene extraction reduced PyOM-C mineralization (R2 = 0.49; P = 0.0006; n = 100). PyOM-C mineralization increased when N atoms were located at the edge of the C network in the form of oxidized N functionalities or when more N was found in PyOM toluene extracts and was more accessible to microbial oxidation. These results confirm the hypothesis that C persistence of fire-derived OM is significantly affected by its molecular N structure and the presented quantitative structure-activity relationship can be utilized for predictive modeling purposes.

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.

Diagnostic accuracy of Xpert MTB/RIF assay and non-molecular methods for the diagnosis of tuberculosis lymphadenitis.

BACKGROUND: Tuberculous lymphadenitis (TBLN) diagnosis remains a challenge in resource limited countries like Ethiopia. Most diagnostic centers in Ethiopia use smear microscopy, but it has low sensitivity in detecting tubercle bacilli in fine needle aspiration (FNA) specimens. FNA cytology (FNAC) is another widely applicable diagnostic option but it has low specificity for diagnosing TBLN. In 2014, WHO recommended Xpert MTB/RIF assay to be used in detecting TB from FNA specimen by considering the diagnostic limitations of microscopy and cytology. In Ethiopia, there is limited data on Xpert MTB/RIF performance in detecting TBLN from FNA. Therefore, this study aimed to evaluate the diagnostic performance of Xpert MTB/RIF assay and non-molecular methods (cytology, microscopy and culture) for the diagnosis of TBLN. METHODS: A cross-sectional study was conducted on 152 presumptive TBLN patients at St. Paul's Hospital Millennium Medical College (SPHMMC) from December 2015 to May 2016 in Addis Ababa, Ethiopia. FNA specimens were collected from each patient. Individual patient specimens were examined by microscopy (acid fast and auramine O staining), cytology, Xpert MTB/RIF and culture. Each specimen was directly inoculated and its sediment following decontamination procedure onto two duplicate Löwenstein-Jensen (LJ) media. Composite culture (specimen positive by direct or concentrated or both culturing methods) and composite method (positive by either one of the non-molecular methods) were taken as reference methods. The data was captured and analyzed using software packages SPSS version 20 (SPSS Inc, Chicago, Illinois, USA). Sensitivity, specificity, positive predictive value, and negative predictive value were calculated. RESULT: A total of 152 presumptive TBLN patients were enrolled in this study. Of these, 105(69%), 68(44.7%), 64(42%), 48(32%) and 33(22%) were positive for M. tuberculosis using composite method (positive by either one of the non-molecular method), composite culture, direct, and concentrated culture, respectively. TB positivity rate was 67.8%, 49.3%, 24.3%, and 14.5% using cytology, Xpert MTB/RIF, Auramine O (FM) microscopy, and Ziehl Nelson (ZN) microscopy, respectively. Using composite culture as reference, the sensitivity and specificity of Xpert MTB/RIF was 78% (95% CI: 73.7% to 82.3%) and 74% (95%CI: 69.4% to 78.6%), respectively. However, the sensitivity of Xpert MTB/RF improved from 78% to 92% using composite method as a reference. The high positivity rate observed in purulent (70%) followed by caseous (66.7%) type of aspirates by Xpert MTB/RIF. CONCLUSION: Xpert MTB/RIF assay has both considerable sensitivity and specificity; it may be employed for better diagnosis, management and treatment of presumptive TBLN patients.

Arbuscular mycorrhizal fungal and soil microbial communities in African Dark Earths.

The socio-economic values of fertile and carbon-rich Dark Earth soils are well described from the Amazon region. Very recently, Dark Earth soils were also identified in tropical West Africa, with comparable beneficial soil properties and plant growth-promoting effects. The impact of this management technique on soil microbial communities, however, is less well understood, especially with respect to the ecologically relevant group of arbuscular mycorrhizal (AM) fungi. Thus, we tested the hypotheses that (1) improved soil quality in African Dark Earth (AfDE) will increase soil microbial biomass and shift community composition and (2) concurrently increased nutrient availability will negatively affect AM fungal communities. Microbial communities were distinct in AfDE in comparison to adjacent sites, with an increased fungal:bacterial ratio of 71%, a pattern mainly related to shifts in pH. AM fungal abundance and diversity, however, did not differ despite clearly increased soil fertility in AfDE, with 3.7 and 1.7 times greater extractable P and total N content, respectively. The absence of detrimental effects on AM fungi, often seen following applications of inorganic fertilizers, and the enhanced role of saprobic fungi relevant for mineralization and C sequestration support previous assertions of this management type as a sustainable alternative agricultural practice.

Micro- and nano-environments of C sequestration in soil: a multi-elemental STXM-NEXAFS assessment of black C and organomineral associations.

Black C is an essential component of the terrestrial C pool and its formation is often credited as a CO(2) sink by transferring the fast-cycling C from the atmosphere-biosphere system into slower cycling C in the geosphere. This study is the first multi-element K- (C, N, Ca, Fe, Al and Si) soft-X-ray STXM-NEXAFS investigation conducted at a submicron-scale spatial resolution specifically targeting black C and its interaction with the mineral and non-black C organic matter in the organomineral assemblage. The STXM-NEXAFS micrographs and spectra demonstrated that pyrogenic C was dominated by quinoide, aromatic, phenol, ketone, alcohol, carboxylic and hydroxylated- and ether-linked C species. There was also evidence for the presence of pyridinic, pyridonic, pyrrolic, amine and nitril N functionalities. The non-black C organic matter contained amino acids, amino sugars, nucleic acids and polysaccharides known to exhibit negatively charged carboxylic, phenolic, enolic, thiolate and phosphate functionalities highly reactive towards metal ions and black C. The metal-rich mineral matrix was composed of phyllosilicate clay minerals, Fe and Al hydroxypolycations, oxides, hydroxides and oxyhydroxide that can attract and bind organic biopolymers. STXM-NEXAFS provided evidence for interactive association between pyrogenic C, non-black C organic matter and the mineral oxide and oxyhydroxide communities in the organomineral interface. These intimate associations occurred through a "two-way" direct linkage between black C and the mineral or non-black C organic matter or via a "three-way" indirect association where non-black C organic matter could serve as a molecular cross-linking agent binding black C with the mineral matrix or vice versa where inorganic oxides, hydroxides and polycations could act as a bridge to bind black C with non-black C organic matter. The binding and sequestration of black C in the investigated micro- and nano-C repository environments seem to be the combined action of physical entrapment in seemingly terminal biotic exclusion zone through the action of metal oxides and organic matter induced microaggregation and through molecular-level association ranging from ligand exchange, polyvalent cation bridging to weak hydrophobic interactions including van der Waals and H-bonding.

Atmospheric SO2 emissions since the late 1800s change organic sulfur forms in humic substance extracts of soils.

Atmospheric SO2 emissions in the UK and globally increased 6- and 20-fold, respectively, from the mid-1800s to the 1960s resulting in increased S deposition, acid rain, and concurrent acidification of terrestrial and aquatic ecosystems. Structural analyses using synchrotron-based X-ray near-edge spectroscopy (XANES) on humic substance extracts of archived samples from the Rothamsted Park Grass Experiment reveal a significant (R2 = -0.58; P < 0.05; N = 7) shift in soil organic sulfur (S) forms, from reduced to more oxidized organic S between 1876 and 1981, even though soil total S contents remained relatively constant. Over the last 30 years, a decrease in emissions and consequent S deposition has again corresponded with a change of organic S structures of humic extracts-reverting in the direction of their early industrial composition. However, the observed reversal lagged behind reductions in emissions by 19 years, which was computed using cross correlations between time series data (R2 = 0.66; P = 0.0024; N = 11). Presently, the ratio of oxidized-to-reduced organic S in humic substance extracts is nearly double that of early industrial times at identical SO2 emission loads. The significant and persistent structural changes of organic S in humic substances as a response to SO2 emissions and S deposition may have effects on recuperation of soils and surface waters from acidification.

Long-term dynamics of phosphorus forms and retention in manure-amended soils.

Phosphorus (P) leaching from soils with elevated P levels due to manure applications is increasingly becoming a concern as a source of eutrophication of streams and lakes. This study investigates the relationship between organic and inorganic P in soil pools and equilibrium leachate along a chronosequence of poultry and dairy manure additions in New York state. Resin-extractable P (molybdate-reactive P, RP) and total soil P reached very high levels of 2330 and 7343 mg of P kg(-1), respectively, after more than 25 years of continuous manure applications. After long-term manuring, the ability of these soils to retain additional P was low (Langmuir maximum sorption potential of 51-59 g of P kg(-1)) and equilibrium leachate concentrations of total dissolved P (TDP) were high (5.5-7.6 mg L(-1); saturated conditions, 0.15-m lysimeters in closed loop). Total dissolved P concentrations in equilibrium leachate increased linearly (r= 0.737) to a total soil P of 4500 mg kg(-1) and increased to a greater extent above 4500-5500 g kg(-1) (change point equivalent to about 1500 mg kg(-1) Mehlich 3-extractable RP). The proportion of dissolved unreactive P (DUP) in equilibrium leachate decreased from 90% of TDP in fields with a short manure application history to 2% of TDP where mainly poultry manure had been applied for >25 years, while unreactive P (UP) in soil decreased from 44% to 6%. Dissolved RP (DRP) was less mobile than DUP in soils with short duration of manure applications (p < 0.05), while differences between DUP and DRP mobility disappeared with longer duration of manure application and greater total soil P. Organic P forms in NaOH/NaF extracts determined by 31P NMR did not change with manure history, but sequential fractionation showed that the relative distribution of RP pools in soils changed. Dilute acid Pi increased from 10% to 62% with longer poultry manure additions, suggesting the formation of calcium phosphates as the soil pH increased from 4.1 to 6.0-7.2. The precipitation of P as calcium phosphates appeared to influence leachable P upon high and long-term applications of manure dominated by poultry litter.

Phosphorus speciation in manure and manure-amended soils using XANES spectroscopy.

Previous studies suggested an increase in the proportion of calcium phosphates (CaP) of the total phosphorus (P) pool in soils with a long-term poultry manure application history versus those with no or limited application histories. To understand and predict long-term P accumulation and release dynamics in these highly amended soils, it is important to understand what specific P species are being formed. We assessed forms of CaP formed in poultry manure and originally acidic soil in response to different lengths of mostly poultry manure applications using P K-edge X-ray absorption near-edge structure (XANES) spectroscopy. Phosphorus K-edge XANES spectra of poultry manure showed no evidences of crystalline P minerals but dominance of soluble CaP species and free and weakly bound phosphates (aqueous phosphate and phosphate adsorbed on soil minerals). Phosphate in an unamended neighboring forest soil (pH 4.3) was mainly associated with iron (Fe) compounds such as strengite and Fe-oxides. Soils with a short-term manure history contained both Fe-associated phosphates and soluble CaP species such as dibasic calcium phosphate (DCP) and amorphous calcium phosphate (ACP). Long-term manure application resulted in a dominance of CaP forms confirming our earlier results obtained with sequential extractions, and a transformation from soluble to more stable CaP species such as beta-tricalcium calcium phosphate (TCP). Even after long-term manure application (> 25 yr and total P in soil up to 13,307 mg kg(-1)), however, none of the manure-amended soils showed the presence of crystalline CaP. With a reduction or elimination of poultry manure application to naturally acidic soils, the pH of the soil is likely to decrease, thereby increasing the solubility of Ca-bonded inorganic P minerals. Maintaining a high pH is therefore an important strategy to minimize P leaching in these soils.