Comparison of Sample Preparation Techniques for the (-)ESI-FT-ICR-MS Analysis of Humic and Fulvic Acids.

Soil organic matter (SOM) plays a key role in the global carbon and nitrogen cycles. Soil biogeochemistry is regularly studied by extracting the base-soluble fractions of SOM: acid-insoluble humic acid (HA) and acid-soluble fulvic acid (FA). Electrospray ionization-Fourier transform-ion cyclotron resonance-mass spectrometry (ESI-FT-ICR-MS) is commonly utilized for molecularly characterizing these fractions. Different sample preparation techniques exist for the analysis of HA and FA though questions remain regarding data comparability following different preparations. Comparisons of different sample preparation techniques here revealed that the negative-mode ESI-FT-ICR-MS analytical window can be skewed to detect different groups of molecules, with primary differences in oxygenation, aromaticity, and molecular weight. It was also observed that HA and FA from soils versus an aquatic matrix behaved very differently. Thus, we conclude that sample preparation techniques determined to be "most optimal" in our study are in no way universal. We recommend that future studies of HA and FA involve similar comparative studies for determining the most suitable sample preparation technique for their particular type of HA or FA matrices. This will enhance data comparability among different studies and environmental systems and ultimately allow us to better understand the complex composition of environmental matrices.

Prediction of enteric methane production and yield in dairy cattle using a Latin America and Caribbean database.

Successful mitigation efforts entail accurate estimation of on-farm emission and prediction models can be an alternative to current laborious and costly in vivo CH4 measurement techniques. This study aimed to: (1) collate a database of individual dairy cattle CH4 emission data from studies conducted in the Latin America and Caribbean (LAC) region; (2) identify key variables for predicting CH4 production (g d-1) and yield [g kg-1 of dry matter intake (DMI)]; (3) develop and cross-validate these newly-developed models; and (4) compare models' predictive ability with equations currently used to support national greenhouse gas (GHG) inventories. A total of 42 studies including 1327 individual dairy cattle records were collated. After removing outliers, the final database retained 34 studies and 610 animal records. Production and yield of CH4 were predicted by fitting mixed-effects models with a random effect of study. Evaluation of developed models and fourteen extant equations was assessed on all-data, confined, and grazing cows subsets. Feed intake was the most important predictor of CH4 production. Our best-developed CH4 production models outperformed Tier 2 equations from the Intergovernmental Panel on Climate Change (IPCC) in the all-data and grazing subsets, whereas they had similar performance for confined animals. Developed CH4 production models that include milk yield can be accurate and useful when feed intake is missing. Some extant equations had similar predictive performance to our best-developed models and can be an option for predicting CH4 production from LAC dairy cows. Extant equations were not accurate in predicting CH4 yield. The use of the newly-developed models rather than extant equations based on energy conversion factors, as applied by the IPCC, can substantially improve the accuracy of GHG inventories in LAC countries.

Structural characterization using 2D NMR spectroscopy and TMAH-GC × GC-MS: Application to humic acids from soils of an integrated agricultural system and an Atlantic native forest.

Understanding the chemical make-up of soils and their structure is critical for constraining the role of soil organic matter (SOM) into the global biogeochemical cycles, as well as to understand the capability of SOM to sequester carbon and mitigate greenhouse gas emissions. Here, we use two-dimensional 1H-13C heteronuclear single quantum coherence nuclear magnetic resonance (2D 1H-13C HSQC NMR) spectroscopy to structurally characterize the most refractory component of SOM, the humic acid (HA). The observations from 2D 1H-13C HSQC NMR were coupled with lignin phenol and fatty acid measurements using tetramethylammonium hydroxide (TMAH) thermochemolysis - two-dimensional gas chromatography - mass spectrometry (TMAH-GC × GC-MS). We studied humic acids extracted from an integrated Crop - Livestock - Forest System (CLFS) agricultural area and an undisturbed Atlantic Native Forest (NF) area. We evaluated soils from two different depths: the topsoil (0-20 cm) and subsoil (60-100 cm) layers, and reveal the presence of oxidized ligninaceous phenols as we had previously hypothesized. Collectively, our results indicate that there are significant oxidative processes with increasing soil depth which are more pronounced in the CLFS relative to the NF area. Degradation of stearic acid with increasing depth in the CLFS soils indicated that the CLFS is more microbiologically active than NF. Therefore, CLFS is less biochemically stable than we originally perceived. The enhanced bio-reactivity of CLFS is likely driving the enhanced carbon sequestration in the CLFS soils. This is perhaps due to the diversity of biomass remnants available at the CLFS soil rhizosphere which allows for more different types of biomass to be sequestered as oxidized ligninaceous phenols. Our results employing structural characterization with 2D 1H-13C HSQC NMR and TMAH-GC × GC-MS provide a new layer of knowledge about the practice of integrated agricultural systems and allow us to understand the structure and fate of sequestered carbon in soils from different soil environments.

Pasture intensification in beef cattle production can affect methane emission intensity.

Increasing greenhouse gas (GHG) emissions from anthropogenic activities have contributed to global warming and consequently to climate change. Among all sources of emissions, the agricultural sector accounts for just under a quarter, mainly because of the intensification of food production systems necessary to supply the growing demand of the population. As ruminal fermentation is the largest source of methane emission in the livestock industry, emission by cattle has become the focus of studies. The aim of this study was to evaluate enteric methane emission and emission intensities of Nellore cattle at different ages submitted to levels of intensification of the grazing system. Twenty-four animals per cycle (age of 21.8 and 13.1 mo in cycles 1 and 2, respectively) were randomly distributed across different grazing systems: irrigated pasture with a high stocking rate (IHS), dryland pasture with a high stocking rate (DHS), recovering dryland pasture with a moderate stocking rate (DMS), and degraded pasture with a low stocking rate (DP). Methane emission was measured using the sulfur hexafluoride technique in each season of the cycle. Intensive systems provided higher yields of good-quality forage as well as superior animal performance when compared with DP. Methane yields were different between seasons and cycles. Methane emissions per average daily weight gain and dry matter digestible intake were different between treatments. Differences in the results were observed when they were analyzed per hectare, with the highest gain yield (P = 0.0134), stocking rate, weight gain, carcass production, and total methane emission (P < 0.0001) being found for the intensive systems. There were no differences in emissions per weight gain or carcass production between production systems, while a difference was observed between cycles (P = 0.0189 and P = 0.0255, respectively), resulting in lower emission intensities for younger animals. We conclude that more intensive systems resulted in a higher kilograms production of carcass per hectare; however, animals at 19 mo of age raised in the IHS and DMS systems had a lower emission intensity in kilogram of CO2-eq. per kilogram of carcass. Moderate intensification (DMS) using animals at about 19 mo of age might be an effective strategy to mitigate GHG emissions from Brazilian tropical pastures. Further studies are needed to understand the relationship between increasing productivity and decreasing environmental impacts, especially methane emission from ruminants.

Strategic grazing management and nitrous oxide fluxes from pasture soils in tropical dairy systems.

Greenhouse gases emissions are considered one of the most important environmental issues of dairy farming systems. Nitrous oxide (N2O) has particular importance owing to its global warming potential and stratospheric ozone depletion. The objective of this study was to investigate the influence of two rotational grazing strategies characterized by two pre-grazing targets (95% and maximum canopy light interception; LI95% and LIMax, respectively) on milk production efficiency and N2O fluxes from soil in a tropical dairy farming system based on elephant grass (Pennisetum purpureum Schum. cv. Cameroon). Results indicated that LI95% pre-grazing target provided more frequent defoliations than LIMax. Water-filled pore space, soil and chamber temperatures were affected by sampling periods (P1 and P2). There was a significant pre-grazing target treatment × sampling period interaction effect on soil NH4+ concentration, which was most likely associated with urinary-N discharge. During P1, there was a greater urinary-N discharge for LI95% than LIMax (26.3 vs. 20.9 kg of urinary-N/paddock) caused by higher stocking rate, which resulted in greater N2O fluxes for LI95%. Inversely, during P2, the soil NH4+ and N2O fluxes were greater for LIMax than LI95%. During this period, the greater urinary-N discharge (46.8 vs. 44.8 kg of urinary-N/paddock) was likely associated with longer stocking period for LIMax relative to LI95%, since both treatments had similar stocking rate. Converting hourly N2O fluxes to daily basis and relating to milk production efficiency, LI95% was 40% more efficient than LIMax (0.34 vs. 0.57 g N-N2O/kg milk·ha). In addition, LI95% pre-grazing target decreased urea-N loading per milk production by 34%. Strategic grazing management represented by the LI95% pre-grazing target allows for intensification of tropical pasture-based dairy systems, enhanced milk production efficiency and decreased N-N2O emission intensity.

Strategic grazing management towards sustainable intensification at tropical pasture-based dairy systems.

Agricultural systems are responsible for environmental impacts that can be mitigated through the adoption of more sustainable principles. Our objective was to investigate the influence of two pre-grazing targets (95% and maximum canopy light interception during pasture regrowth; LI95% and LIMax, respectively) on sward structure and herbage nutritive value of elephant grass cv. Cameroon, and dry matter intake (DMI), milk yield, stocking rate, enteric methane (CH4) emissions by Holstein × Jersey dairy cows. We hypothesized that grazing strategies modifying the sward structure of elephant grass (Pennisetum purpureum Schum.) improves nutritive value of herbage, increasing DMI and reducing intensity of enteric CH4 emissions, providing environmental and productivity benefits to tropical pasture-based dairy systems. Results indicated that pre-sward surface height was greater for LIMax (≈135 cm) than LI95% (≈100 cm) and can be used as a reliable field guide for monitoring sward structure. Grazing management based on LI95% criteria improved herbage nutritive value and grazing efficiency, allowing greater DMI, milk yield and stocking rate by dairy cows. Daily enteric CH4 emission was not affected; however, cows grazing elephant grass at LI95% were more efficient and emitted 21% less CH4/kg of milk yield and 18% less CH4/kg of DMI. The 51% increase in milk yield per hectare overcame the 29% increase in enteric CH4 emissions per hectare in LI95% grazing management. Thereby the same resource allocation resulted in a 16% mitigation of the main greenhouse gas from pasture-based dairy systems. Overall, strategic grazing management is an environmental friendly practice that improves use efficiency of allocated resources through optimization of processes evolving plant, ruminant and their interface, and enhances milk production efficiency of tropical pasture-based systems.