Real-time, high-resolution quantitative measurement of multiple soil gas emissions: selected ion flow tube mass spectrometry

A new technique is presented for the rapid, high-resolution identification and quantification of multiple trace gases above soils, at concentrations down to 0.01 microL L(-1) (10 ppb). The technique, selected ion flow tube mass spectrometry (SIFT-MS), utilizes chemical ionization reagent ions that react with trace gases but not with the major air components (N2, O2, Ar, CO2). This allows the real-time measurement of multiple trace gases without the need for preconcentration, trapping, or chromatographic separation. The technique is demonstrated by monitoring the emission of ammonia and nitric oxide, and the search for volatile organics, above containerized soil samples treated with synthetic cattle urine. In this model system, NH3 emissions peaked after 24 h at 2000 nmol m(-2) s(-1) and integrated to approximately 7% of the urea N applied, while NO emissions peaked about 25 d after urine addition at approximately 140 nmol m(-2) s(-1) and integrated to approximately 10% of the applied urea N. The monitoring of organics along with NH3 and NO was demonstrated in soils treated with synthetic urine, pyridine, and dimethylamine. No emission of volatile nitrogen organics from the urine treatments was observed at levels >0.01% of the applied nitrogen. The SIFT method allows the simultaneous in situ measurement of multiple gas components with a high spatial resolution of < 10 cm and time resolution <20 s. These capabilities allow, for example, identification of emission hotspots, and measurement of localized and rapid variations above agricultural and contaminated soils, as well as integrated emissions over longer periods.     

Dairy farm effluent effects on urine patch nitrous oxide and carbon dioxide emissions

Dairy farm effluent (DFE) comprises animal feces, urine, and wash-down water collected at the milking shed. This is collected daily during the milking season and sprayed onto grazed dairy pastures. Urine patches in grazed pastures make a significant contribution to anthropogenic N(2)O emissions. The DFE could potentially mitigate N(2)O emissions by influencing the N(2)O to dinitrogen (N(2)) ratio, since it contains water-soluble carbon (WSC). Alternatively, DFE may enhance N(2)O emissions from urine patches. The application of DFE may also provide a substrate for the production of CO(2) in pasture soils. The effects of DFE on the CO(2) and N(2)O emissions from urine patches are unknown. Thus a laboratory experiment was performed where repeated DFE applications were made to repacked soil cores. Dairy farm effluent was applied at 0, 7, or 14 d after urine deposition. The urine was applied once on Day 0. Urine contained (15)N-enriched urea. Measurements of N(2)O, N(2), and carbon dioxide (CO(2)) fluxes, soil pH, and soil inorganic N concentrations were made. After 43 d the DFE had not mitigated N(2)O fluxes from urine patches. A small increase in the N(2)O flux occurred from the urine-treated soils where DFE was applied 1 wk after urine deposition. The amount of WSC applied in the DFE proved to be insignificant compared with the amount of soil C released as CO(2) following urine application. The priming of soil C in urine patches has implications for the understanding of soil C processes in grazed pasture ecosystems and the budgeting of C within these ecosystems.     

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

•Addition of hindered amine increased thermal stability and viscosity of TTTM. •Addition of hindered amine improved the CO₂ absorption performance of TTTM. •Good the CO₂ absorption of recycled solvents after two regenerations. •Important role of amine group in CO₂ absorption of TTTM confirmed by DFT analysis. Is it possible to improve CO₂ solubility in potassium carbonate (K₂CO₃)-based transition temperature mixtures (TTMs)? To assess this possibility, a ternary transition-temperature mixture (TTTM) was prepared by using a hindered amine, 2-amino-2-methyl-1,3-propanediol (AMPD). Fourier transform infrared spectroscopy (FT-IR) was employed to detect the functional groups including hydroxyl, amine, carbonate ion, and aliphatic functional groups in the prepared solvents. From thermogravimetric analysis (TGA), it was found that the addition of AMPD to the binary mixture can increase the thermal stability of TTTM. The viscosity findings showed that TTTM has a higher viscosity than TTM while their difference was decreased by increasing temperature. In addition, Eyring’s absolute rate theory was used to compute the activation parameters (ΔG*, ΔH*, and ΔS*). The CO₂ solubility in liquids was measured at a temperature of 303.15 K and pressures up to 1.8 MPa. The results disclosed that the CO₂ solubility of TTTM was improved by the addition of AMPD. At the pressure of about 1.8 MPa, the CO₂ mole fractions of TTM and TTTM were 0.1697 and 0.2022, respectively. To confirm the experimental data, density functional theory (DFT) was employed. From the DFT analysis, it was found that the TTTM+ CO₂ system has higher interaction energy (|ΔE |) than the TTM+ CO₂ system indicating the higher CO₂ affinity of the former system. This study might help scientists to better understand and to improve CO₂ solubility in these types of solvents by choosing a suitable amine as HBD and finding the best combination of HBA and HBD.     

Effects of human footprint and biophysical factors on the body-size structure of fished marine species

Marine fisheries in coastal ecosystems in many areas of the world have historically removed large-bodied individuals, potentially impairing ecosystem functioning and the long-term sustainability of fish populations. Reporting on size-based indicators that link to food-web structure can contribute to ecosystem-based management, but the application of these indicators over large (cross-ecosystem) geographical scales has been limited to either fisheries-dependent catch data or diver-based methods restricted to shallow waters (<20 m) that can misrepresent the abundance of large-bodied fished species. We obtained data on the body-size structure of 82 recreationally or commercially targeted marine demersal teleosts from 2904 deployments of baited remote underwater stereo-video (stereo-BRUV). Sampling was at up to 50 m depth and covered approximately 10,000 km of the continental shelf of Australia. Seascape relief, water depth, and human gravity (i.e., a proxy of human impacts) were the strongest predictors of the probability of occurrence of large fishes and the abundance of fishes above the minimum legal size of capture. No-take marine reserves had a positive effect on the abundance of fishes above legal size, although the effect varied across species groups. In contrast, sublegal fishes were best predicted by gradients in sea surface temperature (mean and variance). In areas of low human impact, large fishes were about three times more likely to be encountered and fishes of legal size were approximately five times more abundant. For conspicuous species groups with contrasting habitat, environmental, and biogeographic affinities, abundance of legal-size fishes typically declined as human impact increased. Our large-scale quantitative analyses highlight the combined importance of seascape complexity, regions with low human footprint, and no-take marine reserves in protecting large-bodied fishes across a broad range of species and ecosystem configurations.     

Predicting tree species presence and basal area in Utah: A comparison of stochastic gradient boosting,generalized additive models,and tree-based methods

Many efforts are underway to produce broad-scale forest attribute maps by modelling forest class and structure variables collected in forest inventories as functions of satellite-based and biophysical information. Typically, variants of classification and regression trees implemented in Rulequest's^© See5 and Cubist (for binary and continuous responses, respectively) are the tools of choice in many of these applications. These tools are widely used in large remote sensing applications, but are not easily interpretable, do not have ties with survey estimation methods, and use proprietary unpublished algorithms. Consequently, three alternative modelling techniques were compared for mapping presence and basal area of 13 species located in the mountain ranges of Utah, USA. The modelling techniques compared included the widely used See5/Cubist, generalized additive models (GAMs), and stochastic gradient boosting (SGB). Model performance was evaluated using independent test data sets. Evaluation criteria for mapping species presence included specificity, sensitivity, Kappa, and area under the curve (AUC). Evaluation criteria for the continuous basal area variables included correlation and relative mean squared error. For predicting species presence (setting thresholds to maximize Kappa), SGB had higher values for the majority of the species for specificity and Kappa, while GAMs had higher values for the majority of the species for sensitivity. In evaluating resultant AUC values, GAM and/or SGB models had significantly better results than the See5 models where significant differences could be detected between models. For nine out of 13 species, basal area prediction results for all modelling techniques were poor (correlations less than 0.5 and relative mean squared errors greater than 0.8), but SGB provided the most stable predictions in these instances. SGB and Cubist performed equally well for modelling basal area for three species with moderate prediction success, while all three modelling tools produced comparably good predictions (correlation of 0.68 and relative mean squared error of 0.56) for one species.     

Ecosystem Modeling Applied to Nutrient Criteria Development in Rivers

Threshold concentrations for biological impairment by nutrients are difficult to quantify in lotic systems, yet States and Tribes in the United States are charged with developing water quality criteria to protect these ecosystems from excessive enrichment. The analysis described in this article explores the use of the ecosystem model AQUATOX to investigate impairment thresholds keyed to biological indexes that can be simulated. The indexes selected for this exercise include percentage cyanobacterial biomass of sestonic algae, and benthic chlorophyll a. The calibrated model was used to analyze responses of these indexes to concurrent reductions in phosphorus, nitrogen, and suspended sediment in an enriched upper Midwestern river. Results suggest that the indexes would respond strongly to changes in phosphorus and suspended sediment, and less strongly to changes in nitrogen concentration. Using simulated concurrent reductions in all three water quality constituents, a total phosphorus concentration of 0.1 mg/l was identified as a threshold concentration, and therefore a hypothetical water quality criterion, for prevention of both excessive periphyton growth and sestonic cyanobacterial blooms. This kind of analysis is suggested as a way to evaluate multiple contrasting impacts of hypothetical nutrient and sediment reductions and to define nutrient criteria or target concentrations that balance multiple management objectives concurrently. Any opinions, findings, conclusions, or recommendations expressed in this article are those of the authors alone, and do not necessarily reflect the views of the U.S. Environmental Protection Agency or of the U.S. Government.     

Nitrous oxide dynamics in a braided river system, New Zealand

Recently the Intergovernmental Panel on Climate Change (IPCC) emission factor EF5-r was revised downward to a value of 0.0025 kg N?O-N per kg NO?-N leached. It was not reduced further due to the continued uncertainty surrounding the dynamics of N?O in river systems. There have been few studies where river system N?O yields and fluxes have been measured. In this study, we examined the relationship between NO?-N and N?O-N fluxes at 10 sites along a braided river system (84 km) over a 397-d period. Isotopic analysis of NO?-N river water samples and the potential agricultural nitrogen (N) sources demonstrated that the NO?-N came from agricultural or sewage sources. Percent saturation of N?O varied with site and date (average, 114%) and correlated with river N?O-N concentrations. Modeled N?O fluxes (16-30 μg m(-2) h(-1)) from five sites were strongly related to river NO?-N concentrations ( r2 = 0.86). The modeled N?O-N fluxes ranged from 39 to 81% of the IPCC-derived emissions based on the NO?-N load in the river over 397 d and do not support further lowering of the EF5-r. Further in situ river studies are required to verify the N?O-N fluxes and the calculated gas transfer velocity values for these braided river systems.     

Role of echinoderms in benthic remineralization in the Chukchi Sea

The role of large, epibenthic organisms in carbon cycling at high latitudes is difficult to assess using standard ship-board collection techniques. We used a remotely operated vehicle equipped with video imaging to examine the distribution and abundance of epibenthic organisms in the northeast Chukchi Sea during June 1998. At each of 11 sites, we collected between 25 and 50 images from a minimum of 20 min of video. We observed 15 different epibenthic taxa, with the echinoderms (Ophiura sarsia, O. maculata, Ophiopholis aculeata, Stegophiura nodosa, and Echinarachinus parma) overwhelmingly dominating the epibenthos. Echinoderm density was highly variable, ranging from 0.2 to 256.6 individuals m^-2 (median=16.3), and echinoderm biomass varied between <0.5 and 4,988 mg C m^-2 (median=737). The highest biomass of ophiuroids recorded (3,388 mg C m^-2) is 30% higher than the highest previously reported from an Arctic shelf. Using a relationship between biomass and respiration developed for deep-sea organisms living at cold temperatures, we estimated respiration rates from <0.1 to 15.0 mg C m^-2 day^-1 (median=1.9). Respiration rates measured on board were several orders of magnitude higher than those obtained from the predictive equation. Further work is needed to assess echinoderm respiration rates accurately under in situ conditions. Even with calculated minimal values for respiration rates, a comparison of epifaunal and infaunal respiration at four stations revealed that echinoderm respiration accounted for as much as 25% of total respiration. High epifaunal respiration rates and biomass values are likely supported by high concentrations of particulate organic carbon carried by Bering Sea water flowing through the eastern Chukchi Sea. Our observations support observations from the Eurasian Arctic that echinoderms dominate the epibenthos of Arctic shelves and that the role of these organisms in carbon remineralization must be considered if we are to generate accurate models of carbon cycling in the Arctic.     

Below-ground nitrogen cycling in relation to net canopy production in mangrove forests of southern Thailand

Rates of accumulation, transformation and availability of sediment nitrogen in four mangrove forests of different age and type in southern Thailand were examined in relation to forest net canopy production. Net ammonification (range: 0.3-2.3 mmol N m^-2 day^-1), nitrification (range: 0-0.7 mmol N m^-2 day^-1) and nitrogen fixation (range: 0-0.6 mmol N m^-2 day^-1) in surface sediments equated to <10% of canopy nitrogen demand (range: 7.5-32 mmol N m^-2 day^-1). By mass balance, we estimated that most of the nitrogen required for tree growth must be derived from root-associated nitrogen fixation and/or mineralisation processes occurring possibly to the maximum depth of live root penetration (75-100 cm). Denitrification, nitrification, rainfall and tidal exchange were comparatively small components of sediment nitrogen flow. Denitrification (range: 0-3.8 mmol N m^-2 day^-1) removed 3-6% of total nitrogen input at three Rhizophora forests, but removed 23% of total nitrogen input in a high-intertidal Ceriops forest. Nitrogen burial ranged from 4% to 12% of total nitrogen input, with the greatest burial rates in two forests receiving the least tidal inundation. Inputs of nitrogen to the forests were rapid (range: 11-37 mmol N m^-2 day^-1), likely originating from upstream sources such as agricultural and industrial lands, sewage and shrimp ponds. Our results indicate that ~70% to 90% of the nitrogen supplied to the forest floor is shunted via the ammonium pool to trees to sustain the rapid rates of net canopy production measured in these forests. Differences in plant-sediment nitrogen relations between the forests appeared to be a function of the interaction between intertidal position and stand age.     

Intensive cattle grazing affects pasture litter-fall: an unrecognized nitrous oxide source

The rationale for this study came from observing grazing dairy cattle dropping freshly harvested plant material onto the soil surface, hereafter called litter-fall. The Intergovernmental Panel on Climate Change (IPCC) guidelines include NO emissions during pasture renewal but do not consider NO emissions that may result from litter-fall. The objectives of this study were to determine litter-fall rates and to assess indicative NO emission factors (EFs) for the dominant pasture species (perennial ryegrass [ L.] and white clover [ L.]). Herbage was vacuumed from intensively managed dairy pastures before and after 30 different grazing events when cows (84 cows ha) grazed for 24 h according to a rotational system; the interval between grazing events ranged from 21 to 30 d. A laboratory incubation study was performed to assess potential EF values for the pasture species at two soil moisture contents. Finely ground pasture material was incubated under controlled laboratory conditions with soil, and the NO emissions were measured until rates returned to control levels. On average, pre- and postgrazing dry matter yields per grazing event were 2516 ± 636 and 1167 ± 265 kg DM ha (±SD), respectively. Pregrazing litter was absent, whereas postgrazing fresh and senesced litter-fall rates were 53 ± 24 and 19 ± 18 kg DM ha, respectively. Annually, the rotational grazing system resulted in 12 grazing events where fresh litter-fall equaed to 16 kg N ha yr to the soil. Emission factors in the laboratory experiment indicated that the EF for perennial ryegrass and white clover ranged from 0.7 to 3.1%. If such EF values should also occur under field conditions, then we estimate that litter-fall induces an NO emission rate of 0.3 kg NO ha yr. Litter-fall as a source of NO in grazed pastures requires further assessment.