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1.
Six sewage sludges from five sewage treatment plants in Australia were characterized using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Spectra were acquired both before and after removal of mineral components through treatment with hydrofluoric acid (HF). Carbon mass balance indicated that little organic matter was lost on HF treatment, which significantly improved NMR sensitivity and spectral resolution, and decreased acquisition time and hence cost of NMR analysis. Two NMR techniques were used, the standard cross polarization (CP) technique and Bloch decay (BD). The BD technique had not been applied previously to the analysis of sewage sludge. For each sludge sample, both before and after HF treatment, the BD spectrum contained significantly more alkyl carbon. Spin counting, another technique applied to sewage sludge here for the first time, showed that the BD spectra of the HF-treated sludges were quantitative, while approximately 30% of the CP NMR signal went undetected. The discrepancy between CP and BD spectra was attributed to the presence of alkyl carbon with such high molecular mobility that the efficiency of cross polarization is affected. This study shows that sewage sludge organic matter is significantly different in chemistry to soil organic matter and has implications for the application of sewage sludge to agricultural land.  相似文献   

2.
Six sewage sludges from five sewage treatment plants in Australia were incubated for up to 21 months. Carbon losses at the end of the 21-mo incubation varied substantially. The remaining organic matter was isolated by treatment with hydrofluoric acid (HF) and characterized using a range of solid-state (13)C nuclear magnetic resonance (NMR) spectroscopic techniques. By every measure (signal distribution in cross polarization [CP] and Bloch decay [BD] spectra, carbon NMR observability determined by spin counting, and the appearance of proton spin relaxation editing subspectra), the chemical composition of the residual organic matter appeared to be little different from that of the original sludges, even for those sludges that experienced the greatest carbon losses. Importantly, these NMR properties distinguish sewage sludge organic matter from soil organic matter. Thus, it should be possible to follow the decomposition of sewage sludge organic matter applied to soils in the field using solid-state (13)C NMR spectroscopy.  相似文献   

3.
The effects of paramagnetic species on solid state 13C nuclear magnetic resonance (NMR) spectra were quantified in a series of doping experiments. The degree of signal loss caused by paramagnetic metals was shown to depend not only on the quantity, but also on the nature of the paramagnetic species, as well as the intimacy of contact with the organic substrate and the type of NMR experiment. Two mechanisms of signal loss were distinguished--signal loss via loss of magnetic field homogeneity, which affects all 13C nuclei in a sample, and signal loss via interaction between electronic and nuclear spins, the effects of which were localized to the close environment of the paramagnetic species. Loss of field homogeneity is important for manganese species, but not for copper species, and is equally important for both cross polarization and Bloch decay experiments. The interaction between electronic and nuclear spins is highly dependent on the spin-lattice relaxation rate constant of the free electron (T1e), as cations with very short T1e values (e.g., Pr3+) cause less signal loss than cations with longer T1e values (e.g., Cu2+, Mn2+). Cross polarization spectra are shown to be more susceptible than Bloch decay spectra to this mechanism of signal loss. Signal loss and increased relaxation rates brought about by paramagnetic species can be used to provide information on soil organic matter (SOM) heterogeneity in the submicron range. This is demonstrated for SOM doped with paramagnetic cations where selective signal loss and increased relaxation rates are used to determine the nature of cation exchange sites.  相似文献   

4.
Microbial breakthrough curves of 12 soils, generated by the application of dairy shed effluent followed by continuous artificial rainfall for one pore volume at 5 mm h(-1) onto large undisturbed soil cores, have been ranked as high, medium, or low potential for microbial bypass flow. The ranking is based on the position of the peak in the breakthrough curve. Knowledge of soil properties that affect microbial transport through soil gained from the microbial breakthrough curves was linked to soil classes, or to their accessory properties, of the New Zealand Soil Classification. Spatial depiction of the ratings has been achieved via the national 1:50,000 scale soil map. Soils with a drainage impediment or those with well developed soil structure have a high potential for microbial bypass flow, whereas soils from tephra and Recent Soils with less developed, porous, soil structure have a low potential for microbial bypass flow. The risk rankings should be considered as maxima because management may change some rankings.  相似文献   

5.
Several solid-state 13C nuclear magnetic resonance (NMR) techniques were used to characterize soil organic matter spiked with 13C-labeled organic compounds spanning a range of hydrophobicities (benzoic acid, benzophenone, naphthalene, phenanthrene, and palmitic acid). The chemical shifts of NMR resonances of the sorbed species were shifted by up to 3 ppm relative to those of the neat compounds. Sorption also resulted in increased resonance linewidth for the compounds containing a single 13C label, indicating the presence of a range of different chemical environments at the sites of sorption. On the other hand, sorption decreased the linewidth of the resonance of naphthalene, which was uniformly 13C-labeled. This was attributed to the removal of intermolecular 13C-13C dipolar coupling. Heterogeneity of the organic matter was demonstrated using the spectral editing technique proton spin relaxation editing (PSRE), which enabled the identification and quantification of charcoal-rich domains characterized by rapid rates of proton spin-lattice relaxation in the static frame (T1H), and humic domains characterized by slow rates of T1H relaxation. Furthermore it was demonstrated that the sorbed 13C-labeled molecules "inherit" the T1H "signature" of the organic matrix in their immediate vicinity. Thus PSRE on the spiked soils enabled evaluation of the relative affinity of the two domain types for the sorbate molecules. The charcoal-rich domains were shown to have a twofold to tenfold greater affinity for the organic compounds, with greater differences found for the more hydrophobic compounds.  相似文献   

6.
Evaluating the impact of land use practices on ground water quality has been difficult because few techniques are capable of monitoring the quality and quantity of soil water flow below the root zone without disturbing the soil profile and affecting natural flow processes. A recently introduced method, known as equilibrium tension lysimetry, was a major improvement but it was not a true equilibrium since it still required manual intervention to maintain proper lysimeter suction. We addressed this issue by developing an automated equilibrium tension lysimeter (AETL) system that continuously matches lysimeter tension to soil-water matric potential of the surrounding soil. The soil-water matric potential of the bulk soil is measured with a heat-dissipation sensor, and a small DC pump is used to apply suction to a lysimeter. The improved automated approach reported here was tested in the field for a 12-mo period. Powered by a small 12-V rechargeable battery, the AETLs were able to continuously match lysimeter suction to soil-water matric potential for 2-wk periods with minimal human attention, along with the added benefit of collecting continuous soil-water matric potential data. We also demonstrated, in the laboratory, methods for continuous measurement of water depth in the AETL, a capability that quantifies drainage on a 10-min interval, making it a true water-flux meter. Equilibrium tension lysimeters have already been demonstrated to be a reliable method of measuring drainage flux, and the further improvements have created a more effective device for studying water drainage and chemical leaching through the soil matrix.  相似文献   

7.
We investigated the seasonal patterns of denitrification rates and potentials in soil profiles along the topohydrosequence formed at the upland-wetland interface in three riparian wetlands with different vegetation cover (i.e., forest, understory vegetation, and grass). Denitrification was measured using the acetylene inhibition method on soil cores and slurries, which provided a means of comparing the relative activity of this process in different locations. We evaluated, on a seasonal basis, the respective importance of the vegetative cover and the hydromorphic gradient as factors limiting denitrification. Regardless of the season, vegetation type, or lateral position along each topohydrosequence in the riparian wetlands, strong significant gradients of both in situ and potential denitrification rates were measured within a soil profile. Results confirm that the upper organic soil horizon is the most active, when in contact with the ground water. In deeper soil horizons, denitrification activity was low (from 0.004 to 0.5 mg N kg(-1) dry soil d(-1)), but contributed significantly to the reduction of ground water NO3- load along the riparian ground water flowpath (from 9.32 to 0.98 mg NO3-N L(-1)). Along the soil topohydrosequence, the denitrifying community of the upper soil horizons did not vary significantly on a seasonal basis despite the large seasonal ground water fluctuations. Along each topohydrosequence, the denitrification-limiting factor gradually shifted from anaerobiosis to NO3- supply. In situ denitrification rates in the forested, understory vegetation and grass sites were not significantly different. This result emphasizes the importance of the topography of the valley rather than the vegetation cover in controlling denitrification activity in riparian wetlands.  相似文献   

8.
Magnetic resonance imaging (MRI) was used to study the flow of water in a column 14 mm in diameter packed with glass heads. The sample was fully saturated and water was pumped through the column using a peristaltic pump, at flow rates of 125 and 250 mL h(-1). This corresponds to mean velocities of 0.5 and 1 mm s(-1), given a porosity of 0.46 m3 m(-3). Nuclear magnetic resonance (NMR) images of the proton density and velocities within a 2-mm slice were taken at a spatial resolution of 0.15 x 0.15 x 2 mm3. At a mean pore water velocity of 1 mm s(-1) we approximated hydrodynamic dispersion using NMR-measured velocity distributions in a 2-mm slice through the sample. Additionally, we conducted a step pulse tracer experiment with chloride through the same column and at identical initial and boundary conditions. We fitted the convection-dispersion equation to the breakthrough curve and compared the column scale dispersion of the tracer experiment with the respective NMR estimate derived at the slice scale.  相似文献   

9.
ABSTRACT: Soil water potentials, slope throughflow, runoff chemistry, and isotopic composition were monitored in a 97 m2 zero-order basin within the Maimai 8 watershed on the South Island of New Zealand, for a natural rain storm and two artificial water applications. Contrary to results previously reported for other portions of the Maimai catchment, much of the runoff occurred as a shallow subsurface organic layer flow. For the 47 mm natural rain event, pre-storm soil matric potential ranged from ?60 to ?150 cm H2O. No saturation was produced within the profile, and the majority of storm runoff emanated from flow within the organic horizon perched on the mineral soil surface. Hillslope applications corroborated this interpretation by showing >90 percent new water flushing with negligible mineral soil moisture response. Although the mechanisms cited in the text are not representative of the entire catchment, the study demonstrates: (1) the value of a combined physical-chemical-isotopic approach in quantifying slope processes, and (2) the heterogeneous nature and diversity of slope runoff pathways in a relatively homogeneous catchment.  相似文献   

10.
Inositol hexakisphosphate (IP6) is often the dominant form of soil organic phosphorus (P), but is rarely investigated because of the analytical difficulties encountered in its extraction, separation, and detection in environmental samples. In particular, recent advances in the study of soil organic P with 31P nuclear magnetic resonance (NMR) have been of limited use for the study of IP6, because the technique does not discriminate between IP6 and other forms of P. This was addressed by developing a novel analytical procedure using the retentive properties of gel-filtration gels for IP6, which allows the combined selective extraction and pre-concentration of IP6 from soil extracts with determination by 31P NMR. While the technique is still in the developmental stage, the results demonstrate that the gel does not interfere with 31P NMR analysis and retains IP6 to concentrations well above those required to give clear spectral signals. The technique has considerable potential for application to the study of IP6 in soil extracts and water samples and, with development, could help to answer fundamental questions regarding the dynamics of organic P in the environment.  相似文献   

11.
The suitability of passive capillary samplers (PCAPS) for collection of representative colloid samples under partially saturated conditions was evaluated by investigating the transport of negatively and positively charged colloids in fiberglass wicks. A synthetic pore water solution was used to suspend silica microspheres (330 nm in diameter) and ferrihydrite (172 nm in diameter) for transport experiments on fiberglass wicks. Breakthrough curves were collected for three unsaturated flow rates with silica microspheres and one unsaturated flow rate with ferrihydrite colloids. A moisture characteristic curve, relating tensiometer measurements of matric potential to moisture content, was developed for the fiberglass wick. Results indicate that retention of the silica and the ferrihydrite on the wick occurred; that is, the wicks did not facilitate quantitative sampling of the colloids. For silica microspheres, 90% of the colloids were transmitted through the wicks. For ferrihydrite, 80 to 90% of the colloids were transmitted. The mechanisms responsible for the retention of the colloids on the fiberglass wicks appeared to be physicochemical attachment and not thin-film, triple-phase entrapment, or mechanical straining. Visualization of pathways by iron staining indicates that flow is preferential at the center of twisted bundles of filaments. Although axial preferential flow in PCAPS may enhance their hydraulic suitability for sampling mobile colloids, we conclude that without specific preparation to reduce attachment or retention, fiberglass wicks should only be used for qualitative sampling of pore water colloids.  相似文献   

12.
Influence of prairie restoration on CT-measured soil pore characteristics   总被引:3,自引:0,他引:3  
Restored prairies are expected to improve soil physical properties, yet little is known about the extent of change to soil properties and how rapidly these changes take place. The objective of this study was to compare effects of prairie restoration on computed tomography (CT)-measured pore parameters. Undisturbed soil cores (76 mm diam. by 76 mm long) from native prairie (NP), restored prairie (RP), conservation reserve program (CRP), and no-till corn (Zea mays L.)-soybean (Glycine max (L.) Merr.; CS) sites were collected with six replicates from the 0- to 40-cm depth in 10-cm increments. Five CT images were acquired from each soil core using a medical CT scanner with 0.2 by 0.2 mm pixel resolution with 0.5 mm slice thickness, and then images were analyzed. Soil bulk density and hydraulic conductivity (K(sat)) were also measured. Soils under NP, RP, CRP, and CS areas had 83, 43, 48, and 26 pores on a 2500 mm(2) area, respectively, for the 0- to 40-cm depth. The number of pores, number of macropores (>1000 microm diam.), macroporosity, mesoporosity (200-1000 microm diam.), and fractal dimension were significantly higher and pore circularity was lower for NP, RP, and CRP than the CS treatment. The CT-measured mesoporosity and macroporosity of the CS treatment were 20 and 18% of the values for the NP site. CT-measured number of pores and macropores explained 43 and 40% of the variation for K(sat). The study showed that prairie restoration improves CT-measured soil pore parameters and decreases bulk density which are related to soil water infiltration.  相似文献   

13.
Adsorption of sulfapyridine, tetracycline, and tylosin to a commercial microporous activated carbon (AC) and its potassium hydroxide (KOH)-, CO-, and steam-treated counterparts (prepared by heating at 850°C) was studied to explore efficient adsorbents for the removal of selected pharmaceuticals from water. Phenol and nitrobenzene were included as additional adsorbates, and nonporous graphite was included as a model adsorbent. The activation treatments markedly increased the specific surface area and enlarged the pore sizes of the mesopores of AC (with the strongest effects shown on the KOH-treated AC). Adsorption of large-size tetracycline and tylosin was greatly enhanced, especially for the KOH-treated AC (more than one order of magnitude), probably due to the alleviated size-exclusion effect. However, the treatments had little effect on adsorption of low-size phenol and nitrobenzene due to the predominance of micropore-filling effect in adsorption and the nearly unaffected content of small micropores causative to such effect. These hypothesized mechanisms on pore-size dependent adsorption were further tested by comparing surface area-normalized adsorption data and adsorbent pore size distributions with and without the presence of adsorbed antibiotics. The findings indicate that efficient adsorption of bulky pharmaceuticals to AC can be achieved by enlarging the adsorbent pore size through suitable activation treatments.  相似文献   

14.
To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.  相似文献   

15.
This article presents several case studies in southwest Germany, which aimed to support land use management decisions by a process-oriented statistical upscaling of point-related environmental monitoring data to the landscape scale. When techniques of data subsetting were used in a sensible way and corresponding to the appropriate scale for the evaluation envisaged, multiple linear regression offered a data mining technique which was able to spatially predict relatively complex environmental patterns with parsimonious, interpretable and accurate models, whereby different evaluation scales were best represented by different DTM resolutions. Scenario models based upon the regression formulas were a valuable tool for visualizing management options and evaluating management impacts (tree species selection) on soil functions (carbon storage), which qualifies the presented methodology as a useful aid in decision making. Such upscaling techniques may be used for forecasting long-term effects of ecosystem management, but they provided no information on temporal dynamics. Therefore, time trends of point information on soil solution data were scaled by linking them to soil chemical data which was available in higher spatial resolution, using both statistical and process-oriented methods.  相似文献   

16.
To test the injection behaviour of CO2 into brine-saturated rock and to evaluate the dependence of geophysical properties on CO2 injection, flow and exposure experiments with brine and CO2 were performed on sandstone samples of the Stuttgart Formation representing potential reservoir rocks for CO2 storage. The sandstone samples studied are generally fine-grained with porosities between 17 and 32% and permeabilities between 1 and 100 mD.Additional batch experiments were performed to predict the long-term behaviour of geological CO2 storage. Reservoir rock samples were exposed over a period of several months to CO2-saturated reservoir fluid in high-pressure vessels under in situ temperature and pressure conditions. Petrophysical parameters, porosity and the pore radius distribution were investigated before and after the experiments by NMR (Nuclear Magnetic Resonance) relaxation and mercury injection. Most of the NMR measurements of the tested samples showed a slight increase of porosity and a higher proportion of large pores.  相似文献   

17.
The environmental fate of herbicides can be studied at different levels: in the lab with disturbed or undisturbed soil columns or in the field with suction cup lysimeters or soil enclosure lysimeters. A field lysimeter experiment with 10 soil enclosures was performed to evaluate the mass balance in different environmental compartments of the phenylurea herbicides diuron [3-(3,4-diclorophenyl)-1,1-dimethyl-urea] and linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea]. After application on the agricultural soil, the herbicides were searched for in soil, pore water, and air samples. Soil and water samples were collected at different depths of the soil profile and analyzed to determine residual concentrations of both the parent compounds and of their main transformation products, to verify their persistence and their leaching capacity. Air volatilization was calculated using the theoretical profile shape method. The herbicides were detected only in the surface layer (0-10 cm) of soil. In this layer, diuron was reduced to 50% of its initial concentration at the end of the experiment, while linuron was still 70% present after 245 d. The main metabolites detected were DCPMU [3-(3,4-dichlorophenyl)-1-methylurea] and DCA (3,4-dichloroaniline). In soil pore water, diuron and linuron were detected at depths of 20 and 40 cm, although in very low concentrations. Therefore the leaching of these herbicides was quite low in this experiment. Moreover, volatilization losses were inconsequential. The calculated total mass balance showed a high persistence of linuron and diuron in the soil, a low mobility in soil pore water (less than 0.5% in leachate water), and a negligible volatilization effect. The application of the Pesticide Leaching Model (PELMO) showed similar low mobility of the chemicals in soil and water, but overestimated their volatilization and their degradation to the metabolite DCPMU. In conclusion, the use of soil enclosure lysimeters proved to be a good experimental design for studying mobility and transport processes of herbicides in field conditions.  相似文献   

18.
Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.  相似文献   

19.
Grain Cd concentrations were determined in the wheat (Triticum aestivum L.) cultivars Soissons, Brigadier, and Hereward grown in 1994,1996, and 1999, respectively, in soils of a long-term field experiment to which sewage sludges contaminated with Zn, Cu, Ni, or Cr had previously been added. Soil pore water soluble Cd and free Cd2+ increased linearly with increasing total soil Cd (R2=0.82 and 0.84, respectively; P<0.001). Similarly, soil pore water free Cd2+ increased linearly with increasing soil pore water soluble Cd (R2=0.98; P<0.001). There was no evidence of a plateau in soil pore water Cd concentrations with increasing soil Cd concentrations. Grain Cd concentrations were significantly correlated with total soil Cd (P<0.001), soil pore water Cd (P<0.001), and free Cd2+ (P<0.001). A slight curvilinear relationship between grain Cd and soil Cd was apparent, but there was no plateau, even at the maximum soil Cd concentration of about 2.7 mg kg(-1). The relationship between soil pore water Cd and grain Cd was linear for all three cultivars. The slopes were in the order 1994 > 1996 > 1999, with more Cd being taken up into the grain by Soissons grown in 1994, and least by Hereward grown in 1999. For Soissons, Cd concentration in the grain greater than the EU limit (0.24 mg kg(-1) dry wt.) occurred at soil Cd less than the current UK limit of 3 mg kg(-1) for soils receiving sewage sludge. In contrast, for Brigadier and Hereward, grain Cd concentrations were near to and less than the EU limit, respectively, at soil Cd concentrations of 3 mg kg(-1).  相似文献   

20.
Abstract: Timber harvest may contribute to increased landsliding frequency through increased soil saturation or loss of soil strength as roots decay. This study assessed the effects of forest harvest on hillslope hydrology and linked hydrologic change before and after harvest with a simple model of hillslope stability. Observations of peak water table heights in 56 ground‐water monitoring wells showed that soil saturation levels on hillslopes differed significantly with harvest intensity at one of the two study locations following 25%, 75%, and 100% harvest. Before the forest was cut 100%, the average rainfall needed for 50% saturation of the soil was 54 mm, but after clearcutting soils reached an equivalent saturation with 61% less rainfall (21 mm). Hillslope stability model results indicate that shallow soils at both study locations, with slopes generally < 30° (58%), were not steep enough to be affected significantly by observed increases in saturation. The stability model indicates that with 100% harvest, there is a 7% reduction in the factor of safety for slope gradients of 35° (70%) with soil depths of 1.25 m. Forest managers may be aided by an understanding that variable hydrologic effects may result from similar forest harvests having different landscape position, land contributing area, and soil depths.  相似文献   

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