Methods for Tier 2 Modeling Within the Training Range Environmental Evaluation and Characterization System

DTIC Science & Technology

2011-03-01

acre-yr, compared with 54 tons/acre-yr as computed with the Universal Soil Loss Equation ( USLE ). Thus, it appears that the Einstein and Brown equations... USLE that is already needed for soil erosion that exports aqueous phase (adsorbed and dissolved) MC. This will mean that solid phase MC will not affect...phase MC mass to soil mass b = soil dry bulk density, g/m3 A = AOI site area, m2 E = soil erosion rate as determined from the USLE , m/yr It is

Determination of Trace Available Heavy Metals in Soil Using Laser-Induced Breakdown Spectroscopy Assisted with Phase Transformation Method.

PubMed

Yi, Rongxing; Yang, Xinyan; Zhou, Ran; Li, Jiaming; Yu, Huiwu; Hao, Zhongqi; Guo, Lianbo; Li, Xiangyou; Lu, Yongfeng; Zeng, Xiaoyan

2018-05-18

To detect available heavy metals in soil using laser-induced breakdown spectroscopy (LIBS) and improve its poor detection sensitivity, a simple and low cost sample pretreatment method named solid-liquid-solid transformation was proposed. By this method, available heavy metals were extracted from soil through ultrasonic vibration and centrifuging and then deposited on a glass slide. Utilization of this solid-liquid-solid transformation method, available Cd and Pb elements in soil were detected successfully. The results show that the regression coefficients of calibration curves for soil analyses reach to more than 0.98. The limits of detection could reach to 0.067 and 0.94 ppm for available Cd and Pb elements in soil under optimized conditions, respectively, which are much better than those obtained by conventional LIBS.

Distribution of Dechlorinating Bacteria between the Aqueous and Solid Phases

NASA Astrophysics Data System (ADS)

Cápiro, N. L.; Hatt, J. K.; Wang, Y.; Loeffler, F. E.; Pennell, K. D.

2010-12-01

Microbial monitoring of aquifers relies on nucleic acid biomarker analysis, which is typically performed with biomass recovered from groundwater samples; however, it is unclear what fraction of the target population(s) is associated with groundwater (i.e., planktonic cells) or is attached to solid phases (i.e., biofilms). Understanding how the titer of target organism(s) in groundwater correlates with the true cell titers of the target organism in the aquifer (i.e., planktonic plus attached cells) is critical for a meaningful interpretation of the data, the prediction of bioremediation performance, and the implementation of site management strategies. To evaluate the distribution of active cells between resident solid phase and the aqueous phase, one-dimensional columns were packed under water-saturated conditions with Bio-Dechlor INOCULUM, a PCE-to ethene-dechlorinating bacterial consortium containing both multiple Dehalococcoides (Dhc) strains and Geobacter lovleyi strain SZ (GeoSZ). The columns were packed with two distinct solid matrices: a low organic content sandy Federal Fine Ottawa soil or Appling soil with higher organic matter content. Influent reduced mineral salts medium supplied at a groundwater pore-water velocity of 0.3 m/day contained both 10 mM lactate as electron donor and 0.33 mM PCE as electron acceptor. Routine collection of biomass from column side ports and effluent samples measured the titers of target cells in the aqueous phase and determined when steady state conditions had been reached. A second set of column experiments evaluated delivery and filtration effects by the solid matrix (i.e., Federal Fine Ottawa sand versus Appling soil) under the same conditions except that electron donor or acceptor were omitted (no growth conditions). Quantitative real-time PCR (qPCR) analysis using Dhc and GeoSZ 16S rRNA gene-targeted primer and probe sets determined the planktonic cell counts, and destructive sampling of the columns allowed measurement of the total cell titer (i.e., attached plus planktonic cells). The results indicate that within the higher organic matter Appling soil, the fraction of target cells associated with the solid phase was nearly 2-orders of magnitude higher compared to the fraction attached to the aqueous phase. In the sandy soil, differences were approximately 1-order of magnitude. Ongoing efforts use dynamic light scattering and electrophoretic mobility measurements over a range of ionic strengths and pH values to shed light on the parameters that control microbial attachment behavior. Knowledge of factors that affect microbial distribution between aqueous and solid phases is essential for interpreting qPCR data obtained from site groundwater where biological remedies are implemented.

Aerodynamic method for obtaining the soil water retention curve

NASA Astrophysics Data System (ADS)

Alekseev, V. V.; Maksimov, I. I.

2013-07-01

A new method for the rapid plotting of the soil water retention curve (SWRC) has been proposed that considers the soil water as an environment limited by the soil solid phase on one side and by the soil air on the other side. Both contact surfaces have surface energies, which play the main role in water retention. The use of an idealized soil model with consideration for the nonequilibrium thermodynamic laws and the aerodynamic similarity principles allows us to estimate the volumetric specific surface areas of soils and, using the proposed pedotransfer function (PTF), to plot the SWRC. The volumetric specific surface area of the solid phase, the porosity, and the specific free surface energy at the water-air interface are used as the SWRC parameters. Devices for measuring the parameters are briefly described. The differences between the proposed PTF and the experimental data have been analyzed using the statistical processing of the data.

COMPARING THE SOLID PHASE AND SALINE EXTRACT MICROTOX(R) ASSAYS FOR TWO PAH CONTAMINATED SOILS

EPA Science Inventory

The performance of remedial treatments is typically evaluated by measuring the concentration of specific chemicals. By adding toxicity bioassays to treatment evaluations, a fuller understanding of treatment performance is obtained. The solid phase Microtox assay is one potenti...

Determination of bentazone, dichlorprop, and MCPA in different soils by sodium hydroxide extraction in combination with solid-phase preconcentration.

PubMed

Thorstensen, C W; Christiansen, A

2001-09-01

A method for the extraction of bentazone, dichlorprop, and MCPA in three selected Norwegian soils of different textures is described. Initially three different extraction methods were tested on one soil type. All methods gave recoveries >80% for the pesticide mixture, but extraction with sodium hydroxide in combination with solid-phase preconcentration was used for further recovery tests with soils of different properties spiked at four herbicide concentration levels (0.001-10 microg/g of wet soil). The method was rapid and easy and required a minimum of organic solvents. The recoveries were in the range of 82-109, 80-123, and 45-91% for the soils containing 1.4 (Hole), 2.5 (Kroer), and 37.8% (Froland) organic carbon, respectively. Limits of quantification using GC-MS were 0.0003 microg/g of wet soil for bentazone and 0.0001 microg/g of wet soil for both dichlorprop and MCPA.

Application of a novel cold activated carbon fiber-solid phase microextraction for analysis of organochlorine pesticides in soil.

PubMed

Chai, Xiaolan; Jia, Jinping; Sun, Tonghua; Wang, Yalin; Liao, Liyan

2007-08-01

A novel and simple analytical procedure using cold activated carbon fiber-solid phase microextraction (CACF-SPME) was applied to determine organochlorine pesticides (OCs) in soil samples. The pesticides in this study consist of alpha -, beta -, gamma -, and delta -hexachlorocyclohexane (HCH). By heating the sample while cooling the fiber, the developed method not only provides better performance in terms of sensitivity, linearity and recovery but also offers shorter adsorption procedure than that of traditional headspace-solid phase microextraction (HS-SPME). The experimental conditions such as the amount of water, adsorption time and adsorption temperature were optimized. Matrix effects were investigated with different types of soils. We concluded that using the standard addition method was required for quantification purposes. The limits of detection obtained using the proposed method range from 0.01 to 0.05 ng/g, and the recoveries for CACF-SPME are in the range of 80.01% to 89.68% with relative standard deviation (RSDs) better than 8.60%. The proposed method was further applied to determine OCs in real agricultural soil. The results are in good agreement with those obtained using traditional ultrasonic extraction. The research demonstrates the suitability of the CACF-SPME for the analysis of OCs in soil.

Determination of Aroclor 1260 in soil samples by gas chromatography with mass spectrometry and solid-phase microextraction.

PubMed

Zhang, Mengliang; Jackson, Glen P; Kruse, Natalie A; Bowman, Jennifer R; Harrington, Peter de B

2014-10-01

A novel fast screening method was developed for the determination of polychlorinated biphenyls that are constituents of the commercial mixture, Aroclor 1260, in soil matrices by gas chromatography with mass spectrometry combined with solid-phase microextraction. Nonequilibrium headspace solid-phase microextraction with a 100 μm polydimethylsiloxane fiber was used to extract polychlorinated biphenyls from 0.5 g of soil matrix. The use of 2 mL of saturated potassium dichromate in 6 M sulfuric acid solution improved the reproducibility of the extractions and the mass transfer of the polychlorinated biphenyls from the soil matrix to the microextraction fiber via the headspace. The extraction time was 30 min at 100°C. The percent recoveries, which were evaluated using an Aroclor 1260 standard and liquid injection, were within the range of 54.9-65.7%. Two-way extracted ion chromatogram data were used to construct calibration curves. The relative error was <±15% and the relative standard deviation was <15%, which are respective measures of the accuracy and precision. The method was validated with certified soil samples and the predicted concentrations for Aroclor 1260 agreed with the certified values. The method was demonstrated to be linear from 10 to 1000 ng/g for Aroclor 1260 in dry soil. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ASSESSING DETOXIFICATION AND DEGRADATION OF WOOD PRESERVING AND PETROLEUM WASTES IN CONTAMINATED SOIL

EPA Science Inventory

This study was undertaken to evaluate in-situ soil bioremediation processes, including degradation and detoxification, for two types of wood preserving wastes and two types of petroleum refining wastes at high concentrations in an unacclimated soil. The soil solid phase, water so...

[Effects of Low-Molecular-Weight Organic Acids on the Speciation of Pb in Purple Soil and Soil Solution].

PubMed

Liu, Jiang; Jiang, Tao; Huang, Rong; Zhang, Jin-zhong; Chen, Hong

2016-04-15

Lead (Pb) in purple soil was selected as the research target, using one-step extraction method with 0.01 mol · L⁻¹ sodium nitrate as the background electrolyte to study the release effect of citric acid (CA), tartaric acid (TA) and acetic acid (AC) with different concentrations. Sequential extraction and geochemical model (Visual Minteq v3.0) were applied to analyze and predict the speciation of Pb in soil solid phase and soil solution phase. Then the ebvironmental implications and risks of low-molecule weight organic acid (LMWOA) on soil Pb were analyzed. The results indicated that all three types of LMWOA increased the desorption capacity of Pb in purple soil, and the effect followed the descending order of CA > TA > AC. After the action of LMWOAs, the exchangeable Pb increased; the carbonate-bound Pb and Fe-Mn oxide bound Pb dropped in soil solid phase. Organic bound Pb was the main speciation in soil solution phase, accounting for 45.16%-75.05%. The following speciation of Pb in soil solution was free Pb, accounting for 22.71%-50.25%. For CA and TA treatments, free Pb ions and inorganic bound Pb in soil solution increased with increasing LMWOAs concentration, while organic bound Pb suffered a decrease in this process. An opposite trend for AC treatment was observed compared with CA and TA treatments. Overall, LMWOAs boosted the bioavailability of Pb in purple soil and had a potential risk to contaminate underground water. Among the three LMWOAs in this study, CA had the largest potential to activate soil Pb.

Iron and aluminum solid phase dynamics and carbon storage across a water balance gradient in volcanic soils

NASA Astrophysics Data System (ADS)

Bateman, J. B.; Fendorf, S. E.; Vitousek, P.

2017-12-01

Iron (Fe) and Aluminum (Al) are major components of volcanic soils, and strongly influence the stability of soil carbon (C). The stability of Fe and Al phases is dictated by the redox conditions and pH of soils, respectively. The water balance of a soil, defined as annual precipitation minus evapotranspiration, ultimately controls pH and redox conditions. Consequently, we hypothesize that water balance influences Fe/Al solid phase dynamics in volcanic soils when the climatic regime has persisted on timescales of 20 ky. To test this hypothesis, we collected soils from a naturally occurring water balance gradient on the windward side of Mauna Kea Volcano in Hawaii, across which water balance ranges from -1270 mm/y to +2000 mm/y. Sampling included complete soil profiles, and 30 cm surface soil samples. We determined the solid phases of Fe/Al with selective extractions and total C via combustion. Extracted Fe/Al were then partitioned into operational pools: organically bound, amorphous, crystalline, primary mineral, primary glass, and residual. All soils in the study were acidic, with pH between 3.4 and 6.4. Soil C varied considerably across the gradient, from <1% C to >15% C by weight. Across sites, soil pH, Fe in primary minerals and glasses, and residual Al are negatively correlated with water balance, while soil C, organic Fe and Al, and crystalline Fe correlated positively with water balance. Organically bound Al increases linearly with water balance, while organically bound Fe is uncorrelated with water balance in soils where water balance is negative and is positively correlated with water balance in wetter sites. These results show that soils developing from the same parent material, though under different water balance regimes, range from lightly weathered ash deposits with little C accumulation in the driest regions, to heavily weathered soils composed of crystalline Fe, organic matter, and organically bound Fe/Al in the wettest regions. Al appears to be the primary stabilizer for organic matter in many of these soils, though Fe plays a role when both water availability and soil C are high. The pattern of organic Fe/Al indicate that pH is a stronger controller on C storage in these soils when water balance is low or negative, and that redox reactions become increasingly important as water balance becomes more positive.

Arbuscular mycorrhizal fungi make a complex contribution to soil aggregation

NASA Astrophysics Data System (ADS)

McGee, Peter; Daynes, Cathal; Damien, Field

2013-04-01

Soil aggregates contain solid and fluid components. Aggregates develop as a consequence of the organic materials, plants and hyphae of arbuscular mycorrhizal (AM) fungi acting on the solid phase. Various correlative studies indicate hyphae of AM fungi enmesh soil particles, but their impact on the pore space is poorly understood. Hyphae may penetrate between particles, remove water from interstitial spaces, and otherwise re-arrange the solid phase. Thus we might predict that AM fungi also change the pore architecture of aggregates. Direct observations of pore architecture of soil, such as by computer-aided tomography (CT), is difficult. The refractive natures of solid and biological material are similar. The plant-available water in various treatments allows us to infer changes in pore architecture. Our experimental studies indicate AM fungi have a complex role in the formation and development of aggregates. Soils formed from compost and coarse subsoil materials were planted with mycorrhizal or non-mycorrhizal seedlings and the resultant soils compared after 6 or 14 months in separate experiments. As well as enmeshing particles, AM fungi were associated with the development of a complex pore space and greater pore volume. Even though AM fungi add organic matter to soil, the modification of pore space is not correlated with organic carbon. In a separate study, we visualised hyphae of AM fungi in a coarse material using CT. In this study, hyphae appeared to grow close to the surfaces of particles with limited ramification across the pore spaces. Hyphae of AM fungi appear to utilise soil moisture for their growth and development of mycelium. The strong correlation between moisture and hyphae has profound implications for soil aggregation, plant utilisation of soil water, and the distribution of water as water availability declines.

Visualising the equilibrium distribution and mobility of organic contaminants in soil using the chemical partitioning space.

PubMed

Wong, Fiona; Wania, Frank

2011-06-01

Assessing the behaviour of organic chemicals in soil is a complex task as it is governed by the physical chemical properties of the chemicals, the characteristics of the soil as well as the ambient conditions of the environment. The chemical partitioning space, defined by the air-water partition coefficient (K(AW)) and the soil organic carbon-water partition coefficient (K(OC)), was employed to visualize the equilibrium distribution of organic contaminants between the air-filled pores, the pore water and the solid phases of the bulk soil and the relative importance of the three transport processes removing contaminants from soil (evaporation, leaching and particle erosion). The partitioning properties of twenty neutral organic chemicals (i.e. herbicides, pharmaceuticals, polychlorinated biphenyls and volatile chemicals) were estimated using poly-parameter linear free energy relationships and superimposed onto these maps. This allows instantaneous estimation of the equilibrium phase distribution and mobility of neutral organic chemicals in soil. Although there is a link between the major phase and the dominant transport process, such that chemicals found in air-filled pore space are subject to evaporation, those in water-filled pore space undergo leaching and those in the sorbed phase are associated with particle erosion, the partitioning coefficient thresholds for distribution and mobility can often deviate by many orders of magnitude. In particular, even a small fraction of chemical in pore water or pore air allows for evaporation and leaching to dominate over solid phase transport. Multiple maps that represent soils that differ in the amount and type of soil organic matter, water saturation, temperature, depth of surface soil horizon, and mineral matters were evaluated.

Micro-scale investigations on soil heterogeneity: Impacts on Zn retention and uptake in Zn contaminated soils

USDA-ARS?s Scientific Manuscript database

Metal contaminants in soils can persist for millennia, causing lasting negative impacts on local ecosystems. Long-term contaminant bioavailability is related to soil pH and the strength and stability of their solid phase associations. We combined physical density separation with synchrotron-based mi...

LINKING SOLID PHASE SPECIATION OF PB SEQUESTERED TO BIRNESSITE TO ORAL PB BIOACCESSIBLITY: IMPLICATIONS FOR SOIL REMEDIATION

EPA Science Inventory

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of lead-contaminated soils. In this study, Pb was sorbed to a model soil mineral, birnessite, and was placed in a simulated gastrointestinal tract (in vitro) to simula...

An Example Emphasizing Mass-Volume Relationships for Problem Solving in Soils

ERIC Educational Resources Information Center

Heitman, J. L.; Vepraskas, M. J.

2009-01-01

Mass-volume relationships are a useful tool emphasized for problem solving in many geo-science and engineering applications. These relationships also have useful applications in soil science. Developing soils students' ability to utilize mass-volume relationships through schematic diagrams of soil phases (i.e., air, water, and solid) can help to…

Toxicity assessment of diesel- and metal-contaminated soils through elutriate and solid phase assays with the slime mold Dictyostelium discoideum.

PubMed

Rodríguez-Ruiz, Amaia; Dondero, Francesco; Viarengo, Aldo; Marigómez, Ionan

2016-06-01

A suite of organisms from different taxonomical and ecological positions is needed to assess environmentally relevant soil toxicity. A new bioassay based on Dictyostelium is presented that is aimed at integrating slime molds into such a testing framework. Toxicity tests on elutriates and the solid phase developmental cycle assay were successfully applied to a soil spiked with a mixture of Zn, Cd, and diesel fuel freshly prepared (recently contaminated) and after 2 yr of aging. The elutriates of both soils provoked toxic effects, but toxicity was markedly lower in the aged soil. In the D. discoideum developmental cycle assay, both soils affected amoeba viability and aggregation, with fewer multicellular units, smaller fruiting bodies and, overall, inhibition of fruiting body formation. This assay is quick and requires small amounts of test soil, which might facilitate its incorporation into a multispecies multiple-endpoint toxicity bioassay battery suitable for environmental risk assessment in soils. Environ Toxicol Chem 2016;35:1413-1421. © 2015 SETAC. © 2015 SETAC.

IMPACT OF CRITICAL ANION SOIL SOLUTION CONCENTRATION ON ALUMINUM ACTIVITY IN ALPINE TUNDRA SOIL Andrew Evans, Jr.1 , Michael B. Jacobs2, and Jason R. Janke1, (1) Metropolitan State University of Denver, Dept. of Earth and Atmospheric Sciences, (2) Dept. of Chemistry, Denver, CO, United States.

NASA Astrophysics Data System (ADS)

Evans, A.

2015-12-01

Soil solution anionic composition can impact both plant and microbial activity in alpine tundra soils by altering biochemical cycling within the soil, either through base cation leaching, or shifts in aluminum controlling solid phases. Although anions play a critical role in the aqueous speciation of metals, relatively few high altitude field studies have examined their impact on aluminum controlling solid phases and aluminum speciation in soil water. For this study, thirty sampling sites were selected on Trail Ridge Road in Rocky Mountain National Park, Estes Park, CO, and sampled during July, the middle of the growing season. Sampling elevations ranged from approximately 3560 - 3710 m. Soil samples were collected to a depth of 15.24 cm, and the anions were extracted using a 2:1 D.I. water to soil ratio. Filtered extracts were analyzed using IC and ICP-MS. Soil solution NO3- concentrations were significantly higher for sampling locations east of Iceberg Pass (EIBP) (mean = 86.94 ± 119.8 mg/L) compared to locations west of Iceberg Pass (WIBP) (mean 1.481 ± 2.444 mg/L). Both F- and PO43- soil solution concentrations, 0.533 and 0.440 mg/L, respectively, were substantially lower, for sampling sites located EIBP, while locations WIBP averaged 0.773 and 0.829 mg/L respectively, for F- and PO43-. Sulfate concentration averaged 3.869 ± 3.059 mg/L for locations EIBP, and 3.891 ± 3.1970 for locations WIBP. Geochemical modeling of Al3+ in the soil solution indicated that a suite of aluminum hydroxyl sulfate minerals controlled Al3+ activity in the alpine tundra soil, with shifts between controlling solid phases occurring in the presence of elevated F- concentrations.

Utilizing thin-film solid-phase extraction to assess the effect of organic carbon amendments on the bioavailability of DDT and dieldrin to earthworms

USDA-ARS?s Scientific Manuscript database

Improved approaches are needed to rapidly and accurately assess the bioavailability of persistent, hydrophobic organic compounds in soils at contaminated sites. The performance of a thin-film solid-phase extraction (TF-SPE) assay using vials coated with ethylene vinyl acetate polymer was compared to...

Organic matter-solid phase interactions are critical for predicting arsenic release and plant uptake in Bangladesh paddy soils.

PubMed

Williams, Paul N; Zhang, Hao; Davison, William; Meharg, Andrew A; Hossain, Mahmud; Norton, Gareth J; Brammer, Hugh; Islam, M Rafiqul

2011-07-15

Agroecological zones within Bangladesh with low levels of arsenic in groundwater and soils produce rice that is high in arsenic with respect to other producing regions of the globe. Little is known about arsenic cycling in these soils and the labile fractions relevant for plant uptake when flooded. Soil porewater dynamics of field soils (n = 39) were recreated under standardized laboratory conditions to investigate the mobility and interplay of arsenic, Fe, Si, C, and other elements, in relation to rice grain element composition, using the dynamic sampling technique diffusive gradients in thin films (DGT). Based on a simple model using only labile DGT measured arsenic and dissolved organic carbon (DOC), concentrations of arsenic in Aman (Monsoon season) rice grain were predicted reliably. DOC was the strongest determinant of arsenic solid-solution phase partitioning, while arsenic release to the soil porewater was shown to be decoupled from that of Fe. This study demonstrates the dual importance of organic matter (OM), in terms of enhancing arsenic release from soils, while reducing bioavailability by sequestering arsenic in solution.

Airborne soil organic particles generated by precipitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Bingbing; Harder, Tristan H.; Kelly, Stephen T.

Airborne organic particles play a critical role in the Earth’s climate1, public health2, air quality3, and hydrological and carbon cycles4. These particles exist in liquid, amorphous semi-solid, or solid (glassy) phase states depending on their composition and ambient conditions5. However, sources and formation mechanisms for semi- solid and solid organic particles are poorly understood and typically neglected in atmospheric models6. Here we report field evidence for airborne solid organic particles generated by a “raindrop” mechanism7 pertinent to atmosphere – land surface interactions (Fig. 1). We find that after rain events at Southern Great Plains, Oklahoma, USA, submicron solid particles, withmore » a composition consistent with soil organic matter, contributed up to 60% of atmospheric particles in number. Subsequent experiments indicate that airborne soil organic particles are ejected from the surface of soils caused by intensive rains or irrigation. Our observations suggest that formation of these particles may be a widespread phenomenon in ecosystems where soils are exposed to strong, episodic precipitation events such as agricultural systems and grasslands8. Chemical imaging and micro-spectroscopy analysis of their physico-chemical properties suggests that airborne soil organic particles may have important impacts on cloud formation and efficiently absorb solar radiation and hence, are an important type of particles.« less

SITE TECHNOLOGY CAPSULE: GRACE DEARBORN INC.'S DARAMEND BIOREMEDIATION TECHNOLOGY

EPA Science Inventory

Grace Dearborn's DARAMEND Bioremediation Technology was developed to treat soils/sediment contaminated with organic contaminants using solid-phase organic amendments. The amendments increase the soil's ability to supply biologically available water/nutrients to microorganisms and...

Impact of soil properties on critical concentrations of cadmium, lead, copper, zinc, and mercury in soil and soil solution in view of ecotoxicological effects.

PubMed

de Vries, Wim; Lofts, Steve; Tipping, Ed; Meili, Markus; Groenenberg, Jan E; Schütze, Gudrun

2007-01-01

Risk assessment for metals in terrestrial ecosystems, including assessments of critical loads, requires appropriate critical limits for metal concentrations in soil and soil solution. This chapter presents an overview of methodologies used to derive critical (i) reactive and total metal concentrations in soils and (ii) free metal ion and total metal concentrations in soil solution for Cd, Pb, Cu, Zn, and Hg, taking into account the effect of soil properties related to ecotoxicological effects. Most emphasis is given to the derivation of critical free and total metal concentrations in soil solution, using available NOEC soil data and transfer functions relating solid-phase and dissolved metal concentrations. This approach is based on the assumption that impacts on test organisms (plants, microorganisms, and soil invertebrates) are mainly related to the soil solution concentration (activity) and not to the soil solid-phase content. Critical Cd, Pb, Cu, Zn, and Hg concentrations in soil solution vary with pH and DOC level. The results obtained are generally comparable to those derived for surface waters based on impacts to aquatic organisms. Critical soil metal concentrations, related to the derived soil solution limits, can be described as a function of pH and organic matter and clay content, and varying about one order of magnitude between different soil types.

Mixed-mode isolation of triazine metabolites from soil and aquifer sediments using automated solid-phase extraction

USGS Publications Warehouse

Mills, M.S.; Thurman, E.M.

1992-01-01

Reversed-phase isolation and ion-exchange purification were combined in the automated solid-phase extraction of two polar s-triazine metabolites, 2-amino-4-chloro-6-(isopropylamino)-s-triazine (deethylatrazine) and 2-amino-4-chloro-6-(ethylamino)-s-triazine (deisopropylatrazine) from clay-loam and slit-loam soils and sandy aquifer sediments. First, methanol/ water (4/1, v/v) soil extracts were transferred to an automated workstation following evaporation of the methanol phase for the rapid reversed-phase isolation of the metabolites on an octadecylresin (C18). The retention of the triazine metabolites on C18 decreased substantially when trace methanol concentrations (1%) remained. Furthermore, the retention on C18 increased with decreasing aqueous solubility and increasing alkyl-chain length of the metabolites and parent herbicides, indicating a reversed-phase interaction. The analytes were eluted with ethyl acetate, which left much of the soil organic-matter impurities on the resin. Second, the small-volume organic eluate was purified on an anion-exchange resin (0.5 mL/min) to extract the remaining soil pigments that could foul the ion source of the GC/MS system. Recoveries of the analytes were 75%, using deuterated atrazine as a surrogate, and were comparable to recoveries by soxhlet extraction. The detection limit was 0.1 ??g/kg with a coefficient of variation of 15%. The ease and efficiency of this automated method makes it viable, practical technique for studying triazine metabolites in the environment.

Assessment of vertical soil solid phase transport (pedoturbations) in different types of land use by magnetic tracer method (Belgorod region, Russia)

NASA Astrophysics Data System (ADS)

Zhidkin, Andrey

2015-04-01

New method of quantitative assessments of vertical soil solid phase transport (pedoturbations) is based on redistribution of spherical magnetic particles (SMP) in soil profiles. SMP - are fly ash components, which mainly produce during coal burning. The main sources of SMP on studied object were locomotives on the railroads, which used coal at the turn of the XIX century. SMP income into the soil only from the atmosphere, very stable for destructions, can be preserved in soils for centuries, and have the same size and weight as the soil matter. So SMP redistribution reflects soil solid phase transport. SMP used as tracers of soil erosion (Olson et.al., 2013), but for the first time applied for quantitative assessments of pedoturbations. In Belgorod region of Russia studied vertical distribution of SMP in soils in different types of land use: a) arable chernozem about 160-year plowing, b) arable chernozem 120-year plowing, c) dark-gray forest soil, which didn't plow at least last 150 years. All three sites are located nearby for the same physical-geography conditions. Distribution of SMP studied layer by layer (thickness of the layer 7 cm) from the top to 70 cm depth, in triplicate soil columns in every land use type (totally 90 soil samples). The period of SMP kept in studied soils is about 115 years. Revealed the different depth of SMP penetration (burial) in soil profiles for this period: 49 cm in the soil of 160-year arable land, 58 cm in the soil of 120-year arable land and 68 cm in the virgin forest soil. Different depth of SMP penetration is connected with different activity of pedoturbations, which differs according to the composition of soil flora and fauna, root activity, and animal mixing work. It is supposed that in the arable land single cropping can reduce the thickness of the active layer and as a result the zone of active pedoturbation depth. Based on SMP distribution counted rates of vertical soil solid phase transport, which are equaled: 31 t/ha/year in the soil of 160-year arable land, 28 t/ha/year in the soil of 120-year arable land, 24 t/ha/year in the virgin forest soil. Certainly raised rates of vertical transport in arable land relative to forest is connected with agricultural plowing. Revealed the connection between the period of plowing and rates of vertical soil transport. Also worth noting is that the rates of pedoturbation in virgin forest soils are rather high and only 1,2-1,3 times less than on arable land uses. This research is funded by Russian Foundation for Basic Research - Project 14-05-31141. 1. Olson K.R., Gennadiyev A.N., Zhidkin A.P., Markelov M.V., Golosov V.N., Lang J.M. Use of magnetic tracer and radio-cesium methods to determine past cropland soil erosion amounts and rates // Catena. - 2013. - V. 104 - P. 103-110.

Mitigation of nonpoint source pollution in rural areas: From control to synergies of multi ecosystem services.

PubMed

Wu, Yonghong; Liu, Junzhuo; Shen, Renfang; Fu, Bojie

2017-12-31

Nonpoint source (NPS) pollution produced by human activities in rural areas has induced excessive nutrient input into surface waters and the decline of water quality. The essence of NPS pollution is the transport of nutrients between soil and water. Traditional NPS pollution control strategies, however, are mainly based on the solid and liquid phases, with little focus on the bio-phase between water and soil. The pollutants produced from NPS can be regarded as a resource if recycled or reused in an appropriate way in the agricultural ecosystem. This mini review proposes novel strategies for NPS pollution control based on three phases (liquid, solid and bio-phase) and highlights the regulating services of an agricultural ecosystem by optimizing land use/cover types. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermal separation of soil particles from thermal conductivity measurement under various air pressures.

PubMed

Lu, Sen; Ren, Tusheng; Lu, Yili; Meng, Ping; Zhang, Jinsong

2017-01-05

The thermal conductivity of dry soils is related closely to air pressure and the contact areas between solid particles. In this study, the thermal conductivity of two-phase soil systems was determined under reduced and increased air pressures. The thermal separation of soil particles, i.e., the characteristic dimension of the pore space (d), was then estimated based on the relationship between soil thermal conductivity and air pressure. Results showed that under both reduced and increased air pressures, d estimations were significantly larger than the geometrical mean separation of solid particles (D), which suggested that conductive heat transfer through solid particles dominated heat transfer in dry soils. The increased air pressure approach gave d values lower than that of the reduced air pressure method. With increasing air pressure, more collisions between gas molecules and solid surface occurred in micro-pores and intra-aggregate pores due to the reduction of mean free path of air molecules. Compared to the reduced air pressure approach, the increased air pressure approach expressed more micro-pore structure attributes in heat transfer. We concluded that measuring thermal conductivity under increased air pressure procedures gave better-quality d values, and improved soil micro-pore structure estimation.

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

PubMed

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

Carbon and Sulfur Isotopic Composition of Rocknest Soil as Determined with the Sample Analysis at Mars(SAM) Quadrupole Mass Spectrometer

NASA Technical Reports Server (NTRS)

Franz, H. B.; McAdam, C.; Stern, J. C.; Archer, P. D., Jr.; Sutter, B.; Grotzinger, J. P.; Jones, J. H.; Leshin, L. A.; Mahaffy, P. R.; Ming, D. W.;

Incubation of air-pollution-control residues from secondary Pb smelter in deciduous and coniferous organic soil horizons: leachability of lead, cadmium and zinc.

PubMed

Chrastný, Vladislav; Vaněk, Aleš; Komárek, Michael; Farkaš, Juraj; Drábek, Ondřej; Vokurková, Petra; Němcová, Jana

2012-03-30

The leachability of air-pollution-control (APC) residues from a secondary lead smelter in organic soil horizons (F and H) from a deciduous and a coniferous forest during incubation periods of 0, 3 and 6 months were compared in this work. While the concentration of Pb, Zn and Cd associated with the exchangeable/acid extractable fraction in the horizon F from the coniferous forest was higher compared to the deciduous, significantly lower concentrations in the humified horizon H was found. It is suggested that lower pH and a higher share of fulvic acids fraction (FAs) of solid phase soil organic matter (SOM) in the humified soil horizon H from the coniferous compared to the deciduous forest is responsible for a higher metal association with solid phase SOM and therefore a lower metal leaching in a soil system. From this point of view, the humified soil horizon H from the deciduous forest represents a soil system more vulnerable to Pb, Zn and Cd leaching from APC residues. Copyright © 2012 Elsevier B.V. All rights reserved.

Organochlorines in surface soil at electronic-waste wire burning sites and metal contribution evaluated using quantitative X-ray speciation

NASA Astrophysics Data System (ADS)

Fujimori, Takashi; Takigami, Hidetaka; Takaoka, Masaki

2013-04-01

Heavy metals and toxic chlorinated aromatic compounds (aromatic-Cls) such as dioxins and polychlorinated biphenyls (PCBs) are found at high concentrations and persist in surface soil at wire burning sites (WBSs) in developing countries in which various wire cables are recycled to yield pure metals. Chlorine K-edge near-edge X-ray absorption fine structure (NEXAFS) is used to detect the specific chemical form of Cl and estimate its amount using a spectrum jump in the solid phase. Quantitative X-ray speciation of Cl was applied to study the mechanisms of aromatic-Cls formation in surface soil at WBSs in Southeast Asia. Relationships between aromatic-Cls and chlorides of heavy metals were evaluated because heavy metals are promoters of the thermochemical solid-phase formation of aromatic-Cls.

Utilizing thin-film solid-phase extraction to assess the effect of organic carbon amendments on the bioavailability of DDT and dieldrin to earthworms

USGS Publications Warehouse

Andrade, Natasha A.; Centofanti, Tiziana; McConnell, Laura L.; Hapeman, Cathleen J.; Torrents, Alba; Anh, Nguyen; Beyer, W. Nelson; Chaney, Rufus L.; Novak, Jeffrey M.; Anderson, Marya O.; Cantrell, Keri B.

2014-01-01

Improved approaches are needed to assess bioavailability of hydrophobic organic compounds in contaminated soils. Performance of thin-film solid-phase extraction (TF-SPE) using vials coated with ethylene vinyl acetate was compared to earthworm bioassay (Lumbricus terrestris). A DDT and dieldrin contaminated soil was amended with four organic carbon materials to assess the change in bioavailability. Addition of organic carbon significantly lowered bioavailability for all compounds except for 4,4′-DDT. Equilibrium concentrations of compounds in the polymer were correlated with uptake by earthworms after 48d exposure (R2 = 0.97; p 40yr of aging. Results show that TF-SPE can be useful in examining potential risks associated with contaminated soils and to test effectiveness of remediation efforts.

SOLID-PHASE TREATMENT OF A PENTACHLOROPHENOL- CONTAMINATED SOIL USING LIGNIN-DEGRADING FUNGI

EPA Science Inventory

The abilities of three lignin-degrading fungi, Phanerochaete chrysosporium, Phanerochaete sordida, and Trametes hirsuta, to deplete pentachlorophenol (PCP) from soil contaminated with PCP and creosote were evaluated. A total of seven fungal and three control treatments ...

Effect of intermediate soil cover on municipal solid waste decomposition.

PubMed

Márquez-Benavides, L; Watson-Craik, I

2003-01-01

A complex series of chemical and microbiological reactions is initiated with the burial of refuse in a sanitary landfill. At the end of each labour day, the municipal solid wastes (MSW) are covered with native soil (or an alternative material). To investigate interaction between the intermediate cover and the MSW, five sets of columns were set up, one packed with refuse only, and four with a soil-refuse mixture (a clay loam, an organic-rich peaty soil, a well limed sandy soil and a chalky soil). The anaerobic degradation over 6 months was followed in terms of leachate volatile fatty acids, chemical oxygen demand, pH and ammoniacal-N performance. Results suggest that the organic-rich peaty soil may accelerate the end of the acidogenic phase. Clay appeared not to have a significant effect on the anaerobic degradation process.

A multi-scale Lattice Boltzmann model for simulating solute transport in 3D X-ray micro-tomography images of aggregated porous materials

NASA Astrophysics Data System (ADS)

Zhang, Xiaoxian; Crawford, John W.; Flavel, Richard J.; Young, Iain M.

2016-10-01

The Lattice Boltzmann (LB) model and X-ray computed tomography (CT) have been increasingly used in combination over the past decade to simulate water flow and chemical transport at pore scale in porous materials. Because of its limitation in resolution and the hierarchical structure of most natural soils, the X-ray CT tomography can only identify pores that are greater than its resolution and treats other pores as solid. As a result, the so-called solid phase in X-ray images may in reality be a grey phase, containing substantial connected pores capable of conducing fluids and solute. Although modified LB models have been developed to simulate fluid flow in such media, models for solute transport are relatively limited. In this paper, we propose a LB model for simulating solute transport in binary soil images containing permeable solid phase. The model is based on the single-relaxation time approach and uses a modified partial bounce-back method to describe the resistance caused by the permeable solid phase to chemical transport. We derive the relationship between the diffusion coefficient and the parameter introduced in the partial bounce-back method, and test the model against analytical solution for movement of a pulse of tracer. We also validate it against classical finite volume method for solute diffusion in a simple 2D image, and then apply the model to a soil image acquired using X-ray tomography at resolution of 30 μm in attempts to analyse how the ability of the solid phase to diffuse solute at micron-scale affects the behaviour of the solute at macro-scale after a volumetric average. Based on the simulated results, we discuss briefly the danger in interpreting experimental results using the continuum model without fully understanding the pore-scale processes, as well as the potential of using pore-scale modelling and tomography to help improve the continuum models.

Variations in the bioavailability of polycyclic aromatic hydrocarbons in industrial and agricultural soils after bioremediation.

PubMed

Guo, Meixia; Gong, Zongqiang; Allinson, Graeme; Tai, Peidong; Miao, Renhui; Li, Xiaojun; Jia, Chunyun; Zhuang, Jie

2016-02-01

The aim of this study was to demonstrate the variations in bioavailability remaining in industrial and agricultural soils contaminated by polycyclic aromatic hydrocarbons (PAHs) after bioremediation. After inoculation of Mycobacterium sp. and Mucor sp., PAH biodegradation was tested on a manufactured gas plant (MGP) soil and an agricultural soil. PAH bioavailability was assessed before and after biodegradation using solid-phase extraction (Tenax-TA extraction) and solid-phase micro-extraction (SPME) to represent bioaccessibility and chemical activity of PAHs, respectively. Only 3- and 4-ring PAHs were noticeably biodegradable in the MGP soil. PAH biodegradation in the agricultural soil was different from that in the MGP soil. The rapidly desorbing fractions (F(rap)) extracted by Tenax-TA and the freely dissolved concentrations of 3- and 4-ring PAHs determined by SPME from the MGP soil decreased after 30 days biodegradation; those values of the 5- and 6-ring PAHs changed to a lesser degree. For the agricultural soil, the F(rap) values of the 3- and 4-ring PAHs also decreased after the biodegradation experiment. The Tenax-TA extraction and the SPME have the potential to assess variations in the bioavailability of PAHs and the degree of biodegradation in contaminated MGP soils. In addition, Tenax-TA extraction is more sensitive than SPME when used in the agricultural soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

SUPERFUND TREATABILITY CLEARINGHOUSE: FINAL REPORT: SOIL TREATMENT PILOT STUDY BRIO/DOP SITE

EPA Science Inventory

Bench and pilot-scale studies were conducted to demonstrate the feasibility of using solid-phase biodegradation for destroying portions of organic constituents present in the soil. The predominant constituents at the BRIO DOP site located in Texas were volatile compounds such...

Microscale Investigations of Soil Heterogeneity: Impacts on Zinc Retention and Uptake in Zinc-Contaminated Soils

DOE PAGES

Rosenfeld, Carla E.; Chaney, Rufus L.; Tappero, Ryan V.; ...

2017-03-17

Here, metal contaminants in soils can persist for millennia, causing lasting negative impacts on local ecosystems. Long-term contaminant bioavailability is related to soil pH and to the strength and stability of solid-phase associations. We combined physical density separation with synchrotron-based microspectroscopy to reduce solid-phase complexity and to study Zn speciation in field-contaminated soils. We also investigated Zn uptake in two Zn-hyperaccumulating ecotypes of Noccaea caerulescens (Ganges and Prayon). Soils were either moderately contaminated (500–800 mg Zn kg –1 via contaminated biosolids application) or grossly enriched (26,000 mg Zn kg –1 via geogenic enrichment). Soils were separated using sodium polytungstate intomore » three fractions: light fraction (LF) (<1.6 g cm –3), medium fraction (MF) (1.6–2.8 g cm –3), and heavy fraction (HF) (>2.8 g cm –3). Approximately 45% of the total Zn was associated with MF in biosolids-contaminated soils. From these data, we infer redistribution to the MF after biosolids application because Zn in biosolids is principally associated with HF and LF. Our results suggest that increasing proportions of HF-associated Zn in soils may be related to greater relative Zn removal by Zn hyperaccumulating plants. Using density fractions enabled assessment of Zn speciation on a microscale despite incomplete fractionation. Analyzing both density fractions and whole soils revealed certain phases (e.g., ZnS, Zn coprecipitated with Fe oxides) that were not obvious in all analyses, indicating multiple views of the same soils enable a more complete understanding of Zn speciation.« less

VARIABLE CHARGE SOILS: MINERALOGY AND CHEMISTRY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Ranst, Eric; Qafoku, Nikolla; Noble, Andrew

2016-09-19

Soils rich in particles with amphoteric surface properties in the Oxisols, Ultisols, Alfisols, Spodosols and Andisols orders (1) are considered to be variable charge soils (2) (Table 1). The term “variable charge” is used to describe organic and inorganic soil constituents with reactive surface groups whose charge varies with pH and ionic concentration and composition of the soil solution. Such groups are the surface carboxyl, phenolic and amino functional groups of organic materials in soils, and surface hydroxyl groups of Fe and Al oxides, allophane and imogolite. The hydroxyl surface groups are also present on edges of some phyllosilicate mineralsmore » such as kaolinite, mica, and hydroxyl-interlayered vermiculite. The variable charge is developed on the surface groups as a result of adsorption or desorption of ions that are constituents of the solid phase, i.e., H+, and the adsorption or desorption of solid-unlike ions that are not constituents of the solid phase. Highly weathered soils and subsoils (e.g., Oxisols and some Ultisols, Alfisols and Andisols) may undergo isoelectric weathering and reach a “zero net charge” stage during their development. They usually have a slightly acidic to acidic soil solution pH, which is close to either the point of zero net charge (PZNC) (3) or the point of zero salt effect (PZSE) (3). They are characterized by high abundances of minerals with a point of zero net proton charge (PZNPC) (3) at neutral and slightly basic pHs; the most important being Fe and Al oxides and allophane. Under acidic conditions, the surfaces of these minerals are net positively charged. In contrast, the surfaces of permanent charge phyllosilicates are negatively charged regardless of ambient conditions. Variable charge soils therefore, are heterogeneous charge systems.« less

Gas chromatographic detection of some nitro explosive compounds in soil samples after solid-phase microextraction with carbon ceramic copper nanoparticle fibers.

PubMed

Farhadi, Khalil; Bochani, Shayesteh; Hatami, Mehdi; Molaei, Rahim; Pirkharrati, Hossein

2014-07-01

In this research, a new solid-phase microextraction fiber based on carbon ceramic composites with copper nanoparticles followed by gas chromatography with flame ionization detection was applied for the extraction and determination of some nitro explosive compounds in soil samples. The proposed method provides an overview of trends related to synthesis of solid-phase microextraction sorbents and their applications in preconcentration and determination of nitro explosives. The sorbents were prepared by mixing of copper nanoparticles with a ceramic composite produced by mixture of methyltrimethoxysilane, graphite, methanol, and hydrochloric acid. The prepared sorbents were coated on copper wires by dip-coating method. The prepared nanocomposites were evaluated statistically and provided better limits of detection than the pure carbon ceramic. The limit of detection of the proposed method was 0.6 μg/g with a linear response over the concentration range of 2-160 μg/g and square of correlation coefficient >0.992. The new proposed fiber has been demonstrated to be a suitable, inexpensive, and sensitive candidate for extraction of nitro explosive compounds in contaminated soil samples. The constructed fiber can be used more than 100 times without the need for surface generation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of an americium solid phase on americium concentrations in solutions

NASA Astrophysics Data System (ADS)

Rai, Dhanpat; Strickert, R. G.; Moore, D. A.; Serne, R. J.

1981-11-01

Americium-241 concentrations in solutions contacting contaminated sediments for up to 2 yr were measured as a function of pH. Steady-state concentrations were reached within a few days. The solubility-limited Am concentration was found to decrease approximately 10-fold with one unit increase in pH. The log equilibrium constant for the solubility of Am (soil) solid [Am (soil) + H + ⇌ Am (aq complex)+] was found to be -4.12. The predictions based upon thermodynamic data suggest that Am (aq complex)+ is likely to be Am(OH) 2+. Although the chemical formula of Am (soil) was not determined, it does not appear to be Am(OH) 3(a). Published data on sorption coefficients of Am by different rocks, soils, and minerals were critically evaluated. Final Am solution concentrations calculated from the sorption coefficients of a variety of earth materials with several solutions agreed well with the concentrations predicted from the solubility of Am (soil) solid, indicating that the sorption coefficient data are controlled by Am precipitation.

Quantification of the vertical translocation rate of soil solid-phase material by the magnetic tracer method

NASA Astrophysics Data System (ADS)

Zhidkin, A. P.; Gennadiev, A. N.

2016-07-01

Approaches to the quantification of the vertical translocation rate of soil solid-phase material by the magnetic tracer method have been developed; the tracer penetration depth and rate have been determined, as well as the radial distribution of the tracer in chernozems (Chernozems) and dark gray forest soils (Luvisols) of Belgorod oblast under natural steppe and forest vegetation and in arable lands under agricultural use of different durations. It has been found that the penetration depth of spherical magnetic particles (SMPs) during their 150-year-occurrence in soils of a forest plot is 68 cm under forest, 58 cm on a 100-year old plowland, and only 49 cm on a 150-year-old plowland. In the chernozems of the steppe plot, the penetration depth of SMPs exceeds the studied depth of 70 cm both under natural vegetation and on the plowlands. The penetration rates of SMPs deep into the soil vary significantly among the key plots: 0.92-1.32 mm/year on the forest plot and 1.47-1.63 mm/year on the steppe plot, probably because of the more active recent turbation activity of soil animals.

Method and apparatus for optimized sampling of volatilizable target substances

DOEpatents

Lindgren, Eric R.; Phelan, James M.

2002-01-01

An apparatus for capturing, from gases such as soil gas, target analytes. Target analytes may include emanations from explosive materials or from residues of explosive materials. The apparatus employs principles of sorption common to solid phase microextraction, and is best used in conjunction with analysis means such as a gas chromatograph. To sorb target analytes, the apparatus functions using various sorptive structures to capture target analyte. Depending upon the embodiment, those structures may include 1) a conventional solid-phase microextraction (SPME) fiber, 2) a SPME fiber suspended in a capillary tube (with means provided for moving gases through the capillary tube so that the gases come into close proximity to the suspended fiber), and 3) a capillary tube including an interior surface on which sorptive material (similar to that on the surface of a SPME fiber) is supported (along with means for moving gases through the capillary tube so that the gases come into close proximity to the sorptive material). In one disclosed embodiment, at least one such sorptive structure is associated with an enclosure including an opening in communication with the surface of a soil region potentially contaminated with buried explosive material such as unexploded ordnance. Emanations from explosive materials can pass into and accumulate in the enclosure where they are sorbed by the sorptive structures. Also disclosed is the use of heating means such as microwave horns to drive target analytes into the soil gas from solid and liquid phase components of the soil.

Geochemical Modeling of Reactions and Partitioning of Trace Metals and Radionuclides during Titration of Contaminated Acidic Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fan; Parker, Jack C.; Luo, Wensui

2008-01-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This study was undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cationmore » exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO{sub 4}{sup 2-} for contaminated sediments indicated close agreement, suggesting that the model could potentially be used to predict the acid-base behavior of the sediment-solution system under variable pH conditions.« less

A whole-cell bioreporter assay for quantitative genotoxicity evaluation of environmental samples.

PubMed

Jiang, Bo; Li, Guanghe; Xing, Yi; Zhang, Dayi; Jia, Jianli; Cui, Zhisong; Luan, Xiao; Tang, Hui

2017-10-01

Whole-cell bioreporters have emerged as promising tools for genotoxicity evaluation, due to their rapidity, cost-effectiveness, sensitivity and selectivity. In this study, a method for detecting genotoxicity in environmental samples was developed using the bioluminescent whole-cell bioreporter Escherichia coli recA::luxCDABE. To further test its performance in a real world scenario, the E. coli bioreporter was applied in two cases: i) soil samples collected from chromium(VI) contaminated sites; ii) crude oil contaminated seawater collected after the Jiaozhou Bay oil spill which occurred in 2013. The chromium(VI) contaminated soils were pretreated by water extraction, and directly exposed to the bioreporter in two phases: aqueous soil extraction (water phase) and soil supernatant (solid phase). The results indicated that both extractable and soil particle fixed chromium(VI) were bioavailable to the bioreporter, and the solid-phase contact bioreporter assay provided a more precise evaluation of soil genotoxicity. For crude oil contaminated seawater, the response of the bioreporter clearly illustrated the spatial and time change in genotoxicity surrounding the spill site, suggesting that the crude oil degradation process decreased the genotoxic risk to ecosystem. In addition, the performance of the bioreporter was simulated by a modified cross-regulation gene expression model, which quantitatively described the DNA damage response of the E. coli bioreporter. Accordingly, the bioluminescent response of the bioreporter was calculated as the mitomycin C equivalent, enabling quantitative comparison of genotoxicities between different environmental samples. This bioreporter assay provides a rapid and sensitive screening tool for direct genotoxicity assessment of environmental samples. Copyright © 2017. Published by Elsevier Ltd.

Fate and lability of silver in soils: Effect of ageing

EPA Science Inventory

The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the ^110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectrosco...

Phase 2, Determining the releasability of the asbestos fiber from soils and solid matrices.

EPA Science Inventory

Factors that affect the releasability or aerosolization of asbestos and related mineral fibers from a variety of sources need to be better understood to allow prediction and modeling of the relative behavior of these fibers. Examples of the sources of concern include soils, roa...

FIELD EVALUATION OF THE LIGNIN-DEGRADING FUNGUS PHANEROCHAETE SORDIDA TO TREAT CREOSOTE-CONTAMINATED SOIL

EPA Science Inventory

A field study to determine the ability of selected lignin-degrading fungi to remediate soil contaminated with creosote was performed at a wood-treating facility in south central Mississippi in the autumn of 1991. The effects of solid-phase bioremediation with Phanerochaete sordid...

Soil solution phosphorus turnover: derivation, interpretation, and insights from a global compilation of isotope exchange kinetic studies

NASA Astrophysics Data System (ADS)

Helfenstein, Julian; Jegminat, Jannes; McLaren, Timothy I.; Frossard, Emmanuel

2018-01-01

The exchange rate of inorganic phosphorus (P) between the soil solution and solid phase, also known as soil solution P turnover, is essential for describing the kinetics of bioavailable P. While soil solution P turnover (Km) can be determined by tracing radioisotopes in a soil-solution system, few studies have done so. We believe that this is due to a lack of understanding on how to derive Km from isotopic exchange kinetic (IEK) experiments, a common form of radioisotope dilution study. Here, we provide a derivation of calculating Km using parameters obtained from IEK experiments. We then calculated Km for 217 soils from published IEK experiments in terrestrial ecosystems, and also that of 18 long-term P fertilizer field experiments. Analysis of the global compilation data set revealed a negative relationship between concentrations of soil solution P and Km. Furthermore, Km buffered isotopically exchangeable P in soils with low concentrations of soil solution P. This finding was supported by an analysis of long-term P fertilizer field experiments, which revealed a negative relationship between Km and phosphate-buffering capacity. Our study highlights the importance of calculating Km for understanding the kinetics of P between the soil solid and solution phases where it is bioavailable. We argue that our derivation can also be used to calculate soil solution turnover of other environmentally relevant and strongly sorbing elements that can be traced with radioisotopes, such as zinc, cadmium, nickel, arsenic, and uranium.

Soil-modified carbon paste electrode: a useful tool in environmental assessment of heavy metal ion binding interactions.

PubMed

Svegl, I G; Ogorevc, B

2000-08-01

Carbon paste electrodes (CPEs) modified with different soils in their native form were prepared to create a soil-like solid phase suitable for application in studies of heavy metal ion uptake and binding interactions. The preparation of CPEs modified with five different soils was examined and their heavy metal ion uptake behavior investigated using a model Cu(II) aqueous solution. Metal ions were accumulated under open circuit conditions and were determined after a medium exchange using differential pulse anodic stripping voltammetry, applying preelectrolysis at -0.7 V. The soil-modified CPE accumulation behavior, including the linearity of the current response versus Cu(II) concentration, the influence of the pH on the solution, and the uptake kinetics, was thoroughly investigated. The correlation between the soil-modified CPE uptake capability and the standard soil parameters, such as ion exchange capacity, soil pH, organic matter and clay content, were evaluated for all five examined soils. The influence of selected endogenous cations (K(I), Ca(II), Fe(III)) on the transfer of Cu(II) ions from a solution to the simulated soil solid phase was examined and is discussed. Preliminary examinations of the soil-modified CPE uptake behavior with some exogenous heavy metal ions of strong environmental interest (Pb(II), Hg(II), Cd(II) and Ag(I)) are also presented. This work demonstrates some attractive possibilities for the application of a soil-modified CPE in studying soil-heavy metal ion binding interactions, with a further potential use as a new environmental sensor appropriate for fist on-site testing of polluted soils.

Comprehensive multiphase NMR spectroscopy: Basic experimental approaches to differentiate phases in heterogeneous samples

NASA Astrophysics Data System (ADS)

Courtier-Murias, Denis; Farooq, Hashim; Masoom, Hussain; Botana, Adolfo; Soong, Ronald; Longstaffe, James G.; Simpson, Myrna J.; Maas, Werner E.; Fey, Michael; Andrew, Brian; Struppe, Jochem; Hutchins, Howard; Krishnamurthy, Sridevi; Kumar, Rajeev; Monette, Martine; Stronks, Henry J.; Hume, Alan; Simpson, André J.

2012-04-01

Heterogeneous samples, such as soils, sediments, plants, tissues, foods and organisms, often contain liquid-, gel- and solid-like phases and it is the synergism between these phases that determine their environmental and biological properties. Studying each phase separately can perturb the sample, removing important structural information such as chemical interactions at the gel-solid interface, kinetics across boundaries and conformation in the natural state. In order to overcome these limitations a Comprehensive Multiphase-Nuclear Magnetic Resonance (CMP-NMR) probe has been developed, and is introduced here, that permits all bonds in all phases to be studied and differentiated in whole unaltered natural samples. The CMP-NMR probe is built with high power circuitry, Magic Angle Spinning (MAS), is fitted with a lock channel, pulse field gradients, and is fully susceptibility matched. Consequently, this novel NMR probe has to cover all HR-MAS aspects without compromising power handling to permit the full range of solution-, gel- and solid-state experiments available today. Using this technology, both structures and interactions can be studied independently in each phase as well as transfer/interactions between phases within a heterogeneous sample. This paper outlines some basic experimental approaches using a model heterogeneous multiphase sample containing liquid-, gel- and solid-like components in water, yielding separate 1H and 13C spectra for the different phases. In addition, 19F performance is also addressed. To illustrate the capability of 19F NMR soil samples, containing two different contaminants, are used, demonstrating a preliminary, but real-world application of this technology. This novel NMR approach possesses a great potential for the in situ study of natural samples in their native state.

Comprehensive multiphase NMR spectroscopy: basic experimental approaches to differentiate phases in heterogeneous samples.

PubMed

Courtier-Murias, Denis; Farooq, Hashim; Masoom, Hussain; Botana, Adolfo; Soong, Ronald; Longstaffe, James G; Simpson, Myrna J; Maas, Werner E; Fey, Michael; Andrew, Brian; Struppe, Jochem; Hutchins, Howard; Krishnamurthy, Sridevi; Kumar, Rajeev; Monette, Martine; Stronks, Henry J; Hume, Alan; Simpson, André J

2012-04-01

Heterogeneous samples, such as soils, sediments, plants, tissues, foods and organisms, often contain liquid-, gel- and solid-like phases and it is the synergism between these phases that determine their environmental and biological properties. Studying each phase separately can perturb the sample, removing important structural information such as chemical interactions at the gel-solid interface, kinetics across boundaries and conformation in the natural state. In order to overcome these limitations a Comprehensive Multiphase-Nuclear Magnetic Resonance (CMP-NMR) probe has been developed, and is introduced here, that permits all bonds in all phases to be studied and differentiated in whole unaltered natural samples. The CMP-NMR probe is built with high power circuitry, Magic Angle Spinning (MAS), is fitted with a lock channel, pulse field gradients, and is fully susceptibility matched. Consequently, this novel NMR probe has to cover all HR-MAS aspects without compromising power handling to permit the full range of solution-, gel- and solid-state experiments available today. Using this technology, both structures and interactions can be studied independently in each phase as well as transfer/interactions between phases within a heterogeneous sample. This paper outlines some basic experimental approaches using a model heterogeneous multiphase sample containing liquid-, gel- and solid-like components in water, yielding separate (1)H and (13)C spectra for the different phases. In addition, (19)F performance is also addressed. To illustrate the capability of (19)F NMR soil samples, containing two different contaminants, are used, demonstrating a preliminary, but real-world application of this technology. This novel NMR approach possesses a great potential for the in situ study of natural samples in their native state. Copyright © 2012 Elsevier Inc. All rights reserved.

Comparative estimation of soil and plant pollution in the impact area of air emissions from an aluminium plant after technogenic load reduction.

PubMed

Evdokimova, Galina A; Mozgova, Natalya P

2015-01-01

The work provides a comparative analysis of changes in soil properties in the last 10-13 years along the pollution gradient of air emissions from Kandalaksha aluminium plant in connection with the reduction of their volume. The content of the priority pollutant fluorine (F) in atmospheric precipitation and in the organic horizon of soil in the plant impact zone significantly decreased in 2011-2013 compared to 2001. The aluminium concentrations reduced only in immediate proximity to the plant (2 km). The fluorine, calcium (Ca) and magnesium (Mg) concentrations are higher in liquid phase compared to solid phase thus these elements can migrated to greater distances from the pollution source (up to 15-20 km). Silicon (Si), aluminium (Al), iron (Fe) and phosphorus (P) can be found only in solid phases and in fall-out within the 5 km. The acidity of soil litter reduced by 2 pH units in the proximity to the plot within the 2 km. The zone of maximum soil contamination decreased from 2.5 km to 1.5 km from the emission source, the zones of heavy and moderate pollution reduced by 5 km in connection with the reduction of pollutant emissions in the plant. A high correlation between the fluorine concentrations in vegetables and litter was found. Higher fluorine concentrations in the soil result in its accumulation in plants. Mosses accumulate fluorine most intensively.

Emerging Environmental Contaminants and Soled Phase Microextraction: Janusz Pawliszyn's Legacy in the Environmental Arena

EPA Science Inventory

Solid phase microextraction (SPME) has revolutionized the way samples are extracted, enabling rapid, automated, and solventless extraction of many different sample types, including air, water, soil, and biological samples. As such, SPME is widely used for environmental, food, fo...

Characterization of interactions between soil solid phase and soil solution in the initial ecosystem development phase

NASA Astrophysics Data System (ADS)

Zimmermann, Claudia; Schaaf, Wolfgang

2010-05-01

In the initial phase of soil formation interactions between solid and liquid phases and processes like mineral weathering, formation of reactive surfaces and accumulation of organic matter play a decisive role in developing soil properties. As part of the Transregional Collaborative Research Centre (SFB/TRR 38) 'Patterns and processes of initial ecosystem development' in an artificial catchment, these interactions are studied at the catchment 'Chicken Creek' (Gerwin et al. 2009). To link the interactions between soil solid phase and soil solution at the micro-scale with observed processes at the catchment scale, microcosm experiments under controlled laboratory conditions were carried out. Main objectives were to determine the transformation processes of C and N from litter decomposition within the gaseous, liquid and solid phase, the interaction with mineral surfaces and its role for the establishment of biogeochemical cycles. The microcosm experiments were established in a climate chamber at constant 10 ° C. In total 48 soil columns (diameter: 14.4 cm; height: 30 cm) were filled with two different quaternary substrates (sand and loamy sand) representing the textural variation within the catchment at a bulk density of 1.4-1.5 g*cm-3. The columns were automatically irrigated four times a day with 6.6 ml each (corresponding to 600 mm*yr-1). The gaseous phase in the headspace of the microcosms was analysed continuously for CO2 and N2O contents. C and N transformation processes were studied using 13C and 15N labelled litter of two different plant species occurring at the catchment (Lotus corniculatus, Calamagrostis epigejos) that was incorporated into the microcosm surface. All treatments including a control ran with four replicates over a period of 40 weeks. Two additional microcosms act as pure litter controls where substrate was replaced by glass pearls. Litter and substrate were analysed before and after the experiment. Percolate was continuously collected and analyzed in two weeks intervals for C and N contents (including δ13C), pH and ion concentrations. The results show that the initial phase of the experiment is characterized by intensive leaching of C and N from the litter and transformation as well as leaching from the substrate. Calcium leaching is caused mainly by carbonate dissolution from the substrates. In contrast, magnesium and especially potassium are leached in initially high amounts from the litter, but are strongly retained in the soil. The addition of litter promotes microbial CO2 production as shown by a strong increase of respiration due to easily available organic substances at the beginning of the experiment. Litter of L. corniculatus induced also a high initial peak in N2O emission as well as higher nitrification and NO3-N leaching. Leaching of DOC and TDN was clearly affected by the substrate texture, illustrated by intensive DOC leaching from the sand at the beginning of the experiment but shifting later to higher leaching rates from the loamy sand. References: Gerwin W, Schaaf W, Biemelt D, Fischer A, Winter S, Hüttl RF (2009) The artificial catchment 'Chicken Creek' (Lusatia, Germany) - a landscape laboratory for interdisciplinary studies of initial ecosystem development. Ecolological Engineering 35, 1786-1796.

Relationship of pyrogenic polycyclic aromatic hydrocarbons contamination among environmental solid media.

PubMed

Kim, Dong Won; Kim, Seung Kyu; Lee, Dong Soo

2009-06-01

This study compared the contamination levels and compositional characteristics of PAHs in soil, SS and sediment to understand the cross media characteristics among the three solid media and ecological risk implications for the purpose to help manage in a more integrated manner the environmental quality objectives or the ecological risk in the media. The study area included urban (metropolis and industrial zone), suburban and rural sites. Seasonal samples were concurrently collected in surface soils, surface waters (dissolved and suspended solid (SS) phases separately) and sediments. The emission estimate and source characterizing PAH indices consistently indicated that PAHs were from pyrogenic sources. The level of total PAHs in soil declined along the wind direction from the urban areas to the rural areas. The sorption power of soil appeared distinctly different between the urban and rural areas. The contamination levels and PAH profiles in soil and sediment were closely related to each other while no such correlation was observed between SS and sediment or SS and soil. Comparisons of the observed partitioning coefficients with three different partitioning equilibrium models strongly suggested that PAHs in water appeared to undergo partitioning among the dissolved phase in water, dissolved organic matter, and organic and soot carbons in SS, which might account for the level and profile of PAHs in SS that were not correlated with those in soil or sediment. The observed results suggested that PAHs of pyrogenic origins entered into soil, sediment, and water by the atmospheric deposition and subsequent other cross-media transfers of PAHs. The results also evidenced that sediments were principally contaminated with PAHs delivered via surface run-off from soil although in the urban areas the run-off influence appeared less immediate than in the rural areas. Environmental quality objectives for PAHs in soil and sediment should be set in a coherent manner and the protection efforts for the sediment quality should be made with the consideration of the soil quality particularly where the river bottom sediment is renewed periodically with eroded soil due to heavy rain and/or large river regime coefficient. In spite of the difference in PAH profiles among the three solid media, BaP commonly appeared to present the greatest TEQ, suggesting that strict regulation of BaP is necessary to efficiently and substantially minimize the total risk of the environmental PAHs.

Increasing Fe0-mediated HMX destruction in highly contaminated soil with didecyldimethylammonium bromide surfactant.

PubMed

Park, Jeong; Comfort, Steve D; Shea, Patrick J; Kim, Jong Sung

2005-12-15

Mixtures of energetic compounds pose a remediation problem for munitions-contaminated soil. Although treatment with zerovalent iron (Fe0) can be effective, RDX and TNT are more readily destroyed than HMX. Adding didecyldimethylammonium bromide (didecyl) at 2% w/v with 3% (w/v) Fe0 to a 20% slurry of Los Alamos National Laboratory soil containing solid-phase HMX (45 000 mg/kg) resulted in >80% destruction within 6 days. Because the HMX concentration did not increase in solution and the didecyl equilibrium concentration was well below the critical micelle concentration, we conclude thatthe solution primarily contained didecyl monomers. The adsorption isotherm for didecyl on iron is consistent with electrostatic adsorption of monomers and some hydrophobic partitioning at low equilibrium concentrations. Fe0 pretreated with didecyl was superior to Fe0 alone or mixed with didecyl in removing HMX from solution, but it was less effective than Fe0 + didecyl when solid-phase HMX was present. Reseeding HMX to mimic dissolution indicated an initial high reactivity of didecyl-pretreated Fe0, but the reaction slowed with each HMX addition. In contrast, reaction rates were lower but reactivity was maintained when Fe0 and didecyl were added together and didecyl was included in fresh HMX solutions. Destruction of solid-phase HMX requires low didecyl concentrations in solution so that hydrophobic patches are maintained on the iron surface.

Solid-phase cadmium speciation in soil using L3-edge XANES spectroscopy with partial least-squares regression.

PubMed

Siebers, Nina; Kruse, Jens; Eckhardt, Kai-Uwe; Hu, Yongfeng; Leinweber, Peter

2012-07-01

Cadmium (Cd) has a high toxicity and resolving its speciation in soil is challenging but essential for estimating the environmental risk. In this study partial least-square (PLS) regression was tested for its capability to deconvolute Cd L(3)-edge X-ray absorption near-edge structure (XANES) spectra of multi-compound mixtures. For this, a library of Cd reference compound spectra and a spectrum of a soil sample were acquired. A good coefficient of determination (R(2)) of Cd compounds in mixtures was obtained for the PLS model using binary and ternary mixtures of various Cd reference compounds proving the validity of this approach. In order to describe complex systems like soil, multi-compound mixtures of a variety of Cd compounds must be included in the PLS model. The obtained PLS regression model was then applied to a highly Cd-contaminated soil revealing Cd(3)(PO(4))(2) (36.1%), Cd(NO(3))(2)·4H(2)O (24.5%), Cd(OH)(2) (21.7%), CdCO(3) (17.1%) and CdCl(2) (0.4%). These preliminary results proved that PLS regression is a promising approach for a direct determination of Cd speciation in the solid phase of a soil sample.

Analysis of Mars analogue soil samples using solid-phase microextraction, organic solvent extraction and gas chromatography/mass spectrometry

NASA Astrophysics Data System (ADS)

Orzechowska, G. E.; Kidd, R. D.; Foing, B. H.; Kanik, I.; Stoker, C.; Ehrenfreund, P.

2011-07-01

Polycyclic aromatic hydrocarbons (PAHs) are robust and abundant molecules in extraterrestrial environments. They are found ubiquitously in the interstellar medium and have been identified in extracts of meteorites collected on Earth. PAHs are important target molecules for planetary exploration missions that investigate the organic inventory of planets, moons and small bodies. This study is part of an interdisciplinary preparation phase to search for organic molecules and life on Mars. We have investigated PAH compounds in desert soils to determine their composition, distribution and stability. Soil samples (Mars analogue soils) were collected at desert areas of Utah in the vicinity of the Mars Desert Research Station (MDRS), in the Arequipa region in Peru and from the Jutland region of Denmark. The aim of this study was to optimize the solid-phase microextraction (SPME) method for fast screening and determination of PAHs in soil samples. This method minimizes sample handling and preserves the chemical integrity of the sample. Complementary liquid extraction was used to obtain information on five- and six-ring PAH compounds. The measured concentrations of PAHs are, in general, very low, ranging from 1 to 60 ng g-1. The texture of soils is mostly sandy loam with few samples being 100 % silt. Collected soils are moderately basic with pH values of 8-9 except for the Salten Skov soil, which is slightly acidic. Although the diverse and variable microbial populations of the samples at the sample sites might have affected the levels and variety of PAHs detected, SPME appears to be a rapid, viable field sampling technique with implications for use on planetary missions.

Analysis of Mars Analogue Soil Samples Using Solid-Phase Microextraction, Organic Solvent Extraction and Gas Chromatography/Mass Spectrometry

NASA Technical Reports Server (NTRS)

Orzechowska, G. E.; Kidd, R. D.; Foing, B. H.; Kanik, I.; Stoker, C.; Ehrenfreund, P.

2011-01-01

Polycyclic aromatic hydrocarbons (PAHs) are robust and abundant molecules in extraterrestrial environments. They are found ubiquitously in the interstellar medium and have been identified in extracts of meteorites collected on Earth. PAHs are important target molecules for planetary exploration missions that investigate the organic inventory of planets, moons and small bodies. This study is part of an interdisciplinary preparation phase to search for organic molecules and life on Mars. We have investigated PAH compounds in desert soils to determine their composition, distribution and stability. Soil samples (Mars analogue soils) were collected at desert areas of Utah in the vicinity of the Mars Desert Research Station (MDRS), in the Arequipa region in Peru and from the Jutland region of Denmark. The aim of this study was to optimize the solid-phase microextraction (SPME) method for fast screening and determination of PAHs in soil samples. This method minimizes sample handling and preserves the chemical integrity of the sample. Complementary liquid extraction was used to obtain information on five- and six-ring PAH compounds. The measured concentrations of PAHs are, in general, very low, ranging from 1 to 60 ng g(sup -1). The texture of soils is mostly sandy loam with few samples being 100% silt. Collected soils are moderately basic with pH values of 8-9 except for the Salten Skov soil, which is slightly acidic. Although the diverse and variable microbial populations of the samples at the sample sites might have affected the levels and variety of PAHs detected, SPME appears to be a rapid, viable field sampling technique with implications for use on planetary missions.

Thermodynamic Investigation of the Effect of Interface Curvature on the Solid-Liquid Equilibrium and Eutectic Point of Binary Mixtures.

PubMed

Liu, Fanghui; Zargarzadeh, Leila; Chung, Hyun-Joong; Elliott, Janet A W

2017-10-12

Thermodynamic phase behavior is affected by curved interfaces in micro- and nanoscale systems. For example, capillary freezing point depression is associated with the pressure difference between the solid and liquid phases caused by interface curvature. In this study, the thermal, mechanical, and chemical equilibrium conditions are derived for binary solid-liquid equilibrium with a curved solid-liquid interface due to confinement in a capillary. This derivation shows the equivalence of the most general forms of the Gibbs-Thomson and Ostwald-Freundlich equations. As an example, the effect of curvature on solid-liquid equilibrium is explained quantitatively for the water/glycerol system. Considering the effect of a curved solid-liquid interface, a complete solid-liquid phase diagram is developed over a range of concentrations for the water/glycerol system (including the freezing of pure water or precipitation of pure glycerol depending on the concentration of the solution). This phase diagram is compared with the traditional phase diagram in which the assumption of a flat solid-liquid interface is made. We show the extent to which nanoscale interface curvature can affect the composition-dependent freezing and precipitating processes, as well as the change in the eutectic point temperature and concentration with interface curvature. Understanding the effect of curvature on solid-liquid equilibrium in nanoscale capillaries has applications in the food industry, soil science, cryobiology, nanoporous materials, and various nanoscience fields.

Determination of parabens and endocrine-disrupting alkylphenols in soil by gas chromatography-mass spectrometry following matrix solid-phase dispersion or in-column microwave-assisted extraction: a comparative study.

PubMed

Pérez, R A; Albero, B; Miguel, E; Sánchez-Brunete, C

2012-03-01

Two rapid methods were evaluated for the simultaneous extraction of seven parabens and two alkylphenols from soil based on matrix solid-phase dispersion (MSPD) and microwave-assisted extraction (MAE). Soil extracts were derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide and analyzed by gas chromatography with mass spectrometry. Extraction and clean-up of samples were carried out by both methods in a single step. A glass sample holder, inside the microwave cell, was used in MAE to allow the simultaneous extraction and clean-up of samples and shorten the MAE procedure. The detection limits achieved by MSPD were lower than those obtained by MAE because the presence of matrix interferences increased with this extraction method. The extraction yields obtained by MSPD and MAE for three different types of soils were compared. Both procedures showed good recoveries and sensitivity for the determination of parabens and alkylphenols in two of the soils assayed, however, only MSPD yielded good recoveries with the other soil. Finally, MSPD was applied to the analysis of soils collected in different sites of Spain. In most of the samples analyzed, methylparaben and butylparaben were detected at levels ranging from 1.21 to 8.04 ng g(-1) dry weight and 0.48 to 1.02 ng g(-1) dry weight, respectively.

Sequential injection system with in-line solid phase extraction and soil mini-column for determination of zinc and copper in soil leachates.

PubMed

Paluch, Justyna; Mesquita, Raquel B R; Cerdà, Víctor; Kozak, Joanna; Wieczorek, Marcin; Rangel, António O S S

2018-08-01

A sequential injection (SI) system equipped with in-line solid phase extraction column and in-line soil mini-column is proposed for determination of zinc and copper in soil leachates. The spectrophotometric determination (560 nm) is based on the reaction of both analytes with 1-(2-Pyridylazo)-2-naphthol (PAN). Zinc is determined after retaining copper on a cationic resin (Chelex100) whereas copper is determined from the difference of the absorbance measured for both analytes, introduced into the system with the use of a different channel, and zinc absorbance. The influence of several potential interferences was studied. Using the developed method, zinc and copper were determined within the concentration ranges of 0.005-0.300 and 0.011-0.200 mg L -1 , and with a relative standard deviation lower than 6.0% and 5.1%, respectively. The detection limits are 1.4 and 3.0 µg/L for determination of zinc and copper, respectively. The developed SI method was verified by the determination of both analytes in synthetic and certified reference materials of water samples, and applied to the determination of the analytes in rain water and soil leachates from laboratory scale soil core column and in-line soil mini-column. Copyright © 2018 Elsevier B.V. All rights reserved.

From solid to liquid: Assessing the release of carbon from soil into solution in response to forest management

NASA Astrophysics Data System (ADS)

James, J. N.; Gross, C. D.; Butman, D. E.; Harrison, R. B.

2016-12-01

Dissolved organic matter (DOM) is a crucial conduit for internal cycling of carbon within soils as well as for the transfer of organic matter out of soil and into aquatic systems. Little is known about how the quantity, quality, lability and chemical characteristics of DOM changes in response to human management of forest soils. To examine the processes that release soil organic matter (SOM) into solution, we gathered samples from adjacent native and industrially managed Eucalyptus grandis plantation forests across Sao Paulo State, Brazil and from adjacent old-growth and Douglas-fir (Pseudotsuga menzisii) plantation forests in the coastal Pacific Northwest. Samples from each soil horizon were taken from soil profiles excavated to at least 1.5 m at each site. Water extractable organic matter (WEOM) was extracted twice from each sample using 0.5 M K2SO4 and Milli-Q water to quantify both dissolved and exchange phase organic matter. These extracts were measured for total organic carbon (TOC), 13C and 14C, and chemical characteristics were assessed by fluorescence spectroscopy (EEMs and SUVA254). At the same time, solid phase characteristics of the soil samples were quantified, including bulk density, pH, total carbon and nitrogen, microbial biomass, and 13C and 14C. Characterization of bulk SOM was undertaken by Fourier Transform Infrared Spectroscopy (FTIR) by subtracting mineral matrix spectra of each sample from the bulk spectra. Organic matter lability was assessed by incubations using difference in TOC for WEOM extracts and repeated measurement of CO2 efflux for bulk SOM. All together, these analyses permit a unique snapshot of the natural separation of organic matter from solid into liquid phase through the entire soil profile. Initial results reveal that small but measureable quantities of WEOM may be released from deep B and C horizons in soil, and that this material is labile to microbial decomposition. By identifying differences in SOM and DOM cycling due to forest management, this study aims to connect human management of terrestrial forest ecosystems to the transport of organic matter from surface and subsurface horizons to freshwater ecosystems, where it forms a major component of aquatic food webs.

Rapid determination of the volatile components in tobacco by ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction with gas chromatography-mass spectrometry.

PubMed

Yang, Yanqin; Chu, Guohai; Zhou, Guojun; Jiang, Jian; Yuan, Kailong; Pan, Yuanjiang; Song, Zhiyu; Li, Zuguang; Xia, Qian; Lu, Xinbo; Xiao, Weiqiang

2016-03-01

An ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction was first employed to determine the volatile components in tobacco samples. The method combined the advantages of ultrasound, microwave, and headspace solid-phase microextraction. The extraction, separation, and enrichment were performed in a single step, which could greatly simplify the operation and reduce the whole pretreatment time. In the developed method, several experimental parameters, such as fiber type, ultrasound power, and irradiation time, were optimized to improve sampling efficiency. Under the optimal conditions, there were 37, 36, 34, and 36 components identified in tobacco from Guizhou, Hunan, Yunnan, and Zimbabwe, respectively, including esters, heterocycles, alkanes, ketones, terpenoids, acids, phenols, and alcohols. The compound types were roughly the same while the contents were varied from different origins due to the disparity of their growing conditions, such as soil, water, and climate. In addition, the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction method was compared with the microwave-assisted extraction coupled to headspace solid-phase microextraction and headspace solid-phase microextraction methods. More types of volatile components were obtained by using the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction method, moreover, the contents were high. The results indicated that the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction technique was a simple, time-saving and highly efficient approach, which was especially suitable for analysis of the volatile components in tobacco. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of trichloroethylene cometabolism and toluene biodegradation: Model application to soil batch experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

El-Farhan, Y.H.; Scow, K.M.; Fan, S.

Trichloroethylene (TCE) biodegradation in soil under aerobic conditions requires the presence of another compound, such as toluene, to support growth of microbial populations and enzyme induction. The biodegradation kinetics of TCE and toluene were examined by conducting three groups of experiments in soil: toluene only, toluene combined with low TCE concentrations, and toluene with TCE concentrations similar to or higher than toluene. The biodegradation of TCE and toluene and their interrelationships were modeled using a combination of several biodegradation functions. In the model, the pollutants were described as existing in the solid, liquid, and gas phases of soil, with biodegradationmore » occurring only in the liquid phase. The distribution of the chemicals between the solid and liquid phase was described by a linear sorption isotherm, whereas liquid-vapor partitioning was described by Henry's law. Results from 12 experiments with toluene only could be described by a single set of kinetic parameters. The same set of parameters could describe toluene degradation in 10 experiments where low TCE concentrations were present. From these 10 experiments a set of parameters describing TCE cometabolism induced by toluene also was obtained. The complete set of parameters was used to describe the biodegradation of both compounds in 15 additional experiments, where significant TCE toxicity and inhibition effects were expected. Toluene parameters were similar to values reported for pure culture systems. Parameters describing the interaction of TCE with toluene and biomass were different from reported values for pure cultures, suggesting that the presence of soil may have affected the cometabolic ability of the indigenous soil microbial populations.« less

Leaching of copper and nickel in soil-water systems contaminated by bauxite residue (red mud) from Ajka, Hungary: the importance of soil organic matter.

PubMed

Lockwood, Cindy L; Stewart, Douglas I; Mortimer, Robert J G; Mayes, William M; Jarvis, Adam P; Gruiz, Katalin; Burke, Ian T

2015-07-01

Red mud is a highly alkaline (pH >12) waste product from bauxite ore processing. The red mud spill at Ajka, Hungary, in 2010 released 1 million m(3) of caustic red mud into the surrounding area with devastating results. Aerobic and anaerobic batch experiments and solid phase extraction techniques were used to assess the impact of red mud addition on the mobility of Cu and Ni in soils from near the Ajka spill site. Red mud addition increases aqueous dissolved organic carbon (DOC) concentrations due to soil alkalisation, and this led to increased mobility of Cu and Ni complexed to organic matter. With Ajka soils, more Cu was mobilised by contact with red mud than Ni, despite a higher overall Ni concentration in the solid phase. This is most probably because Cu has a higher affinity to form complexes with organic matter than Ni. In aerobic experiments, contact with the atmosphere reduced soil pH via carbonation reactions, and this reduced organic matter dissolution and thereby lowered Cu/Ni mobility. These data show that the mixing of red mud into organic rich soils is an area of concern, as there is a potential to mobilise Cu and Ni as organically bound complexes, via soil alkalisation. This could be especially problematic in locations where anaerobic conditions can prevail, such as wetland areas contaminated by the spill.

Control of arsenic mobilization in paddy soils by manganese and iron oxides.

PubMed

Xu, Xiaowei; Chen, Chuan; Wang, Peng; Kretzschmar, Ruben; Zhao, Fang-Jie

2017-12-01

Reductive mobilization of arsenic (As) in paddy soils under flooded conditions is an important reason for the relatively high accumulation of As in rice, posing a risk to food safety and human health. The extent of As mobilization varies widely among paddy soils, but the reasons are not well understood. In this study, we investigated As mobilization in six As-contaminated paddy soils (total As ranging from 73 to 122 mg kg -1 ) in flooded incubation and pot experiments. Arsenic speciation in the solution and solid phases were determined. The magnitude of As mobilization into the porewater varied by > 100 times among the six soils. Porewater As concentration correlated closely with the concentration of oxalate-extractable As, suggesting that As associated with amorphous iron (oxyhydr)oxides represents the potentially mobilizable pool of As under flooded conditions. Soil containing a high level of manganese oxides showed the lowest As mobilization, likely because Mn oxides retard As mobilization by slowing down the drop of redox potential upon soil flooding and maintaining a higher arsenate to arsenite ratio in the solid and solution phases. Additions of a synthetic Mn oxide (hausmannite) to two paddy soils increased arsenite oxidation, decreased As mobilization into the porewater and decreased As concentrations in rice grain and straw. Consistent with previous studies using simplified model systems or pure mineral phases, the present study shows that Mn oxides and amorphous Fe (oxyhydr)oxides are important factors controlling reductive As mobilization in As-contaminated paddy soils. In addition, this study also suggests a potential mitigation strategy using exogenous Mn oxides to decrease As uptake by rice in paddy soils containing low levels of indigenous Mn oxides, although further work is needed to verify its efficacy and possible secondary effects under field conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heavy metals in Iberian soils: Removal by current adsorbents/amendments and prospective for aerogels.

PubMed

Vareda, João P; Valente, Artur J M; Durães, Luisa

2016-11-01

Heavy metals are dangerous pollutants that in spite of occurring naturally are released in major amounts to the environment due to anthropogenic activities. After being released in the environment, the heavy metals end up in the soils where they accumulate as they do not degrade, adversely affecting the biota. Because of the dynamic equilibria between soil constituents, the heavy metals may be present in different phases such as the solid phase (immobilized contaminants) or dissolved in soil solution. The latter form is the most dangerous because the ions are mobile, can leach and be absorbed by living organisms. Different methods for the decontamination of polluted soils have been proposed and they make use of two different approaches: mobilizing the heavy metals, which allows their removal from soil, or immobilization that maintains the metal concentrations in soils but keeps them in an inert form due to mechanisms like precipitation, complexation or adsorption. Mobilization of the heavy metals is known to cause leaching and increase plant uptake, so this treatment can cause greater problems. Aerogels are incredible nanostructured, lightweight materials with high surface area and tailorable surface chemistry. Their application in environmental cleaning has been increasing in recent years and very promising results have been obtained. The functionalization of the aerogels can give them the ability to interact with heavy metals, retaining the latter via strong adsorptive interactions. Thus, this review surveys the existing literature for remediation of soils using an immobilization approach, i.e. with soil amendments that increase the soil sorption/retention capacity for heavy metals. The considered framework was a set of heavy metals with relevance in polluted Iberian soils, namely Cd, Cr, Cu, Ni, Pb and Zn. Moreover, other adsorbents, especially aerogels, have been used for the removal of these contaminants from aqueous media; because groundwater and soil solution have dynamic equilibria with the soil solid phase, these works allowed to draw conclusions and perspectives for the use of aerogels not only as adsorbents in aqueous media but also as amendments for the remediation of heavy metal polluted soils. Copyright © 2016 Elsevier B.V. All rights reserved.

Erosion and physical transport via overland flow of arsenic and lead bound to silt-sized particles

PubMed Central

Cadwalader, G. Owen; Renshaw, Carl E.; Jackson, Brian P.; Magilligan, Francis J.; Landis, Joshua D.; Bostick, Benjamin C.

2011-01-01

Understanding of the transport mechanisms of contaminated soils and sediment is essential for the sustainable management of contaminated lands. In New England and elsewhere, vast areas of agricultural lands are contaminated by the historical application of lead-arsenate pesticides. Left undisturbed the physical and chemical mobility of As and Pb in these soils is limited due to their strong affinity for adsorption onto solid phases. However, soil disturbance promotes erosion and overland flow during intense rainstorms. Here we investigate the event-scale transport of disturbed As and Pb contaminated soils through measurement of concentrations of As and Pb in suspended sediment and changes in Pb isotopic ratios in overland flow. Investigation of several rain events shows that where land disturbance has occurred, physical transport of silt-sized particles and aggregates is the primary transport vector of As and Pb derived from pesticide-contaminated soil. Although both As and Pb are associated with similarly-sized particles, we find that solid-phase As is more effectively mobilized and transported than Pb. Our results demonstrate that anthropogenic land disturbance of historical lands contaminated with lead-arsenate pesticides may redistribute, through physical transport, significant amounts of As, and lesser amounts of Pb, to riparian and stream sediments, where they are potentially more bioavailable. PMID:21552357

Dispersive solid-phase extraction followed by vortex-assisted dispersive liquid-liquid microextraction based on the solidification of a floating organic droplet for the determination of benzoylurea insecticides in soil and sewage sludge.

PubMed

Peng, Guilong; He, Qiang; Mmereki, Daniel; Lu, Ying; Zhong, Zhihui; Liu, Hanyang; Pan, Weiliang; Zhou, Guangming; Chen, Junhua

2016-04-01

A novel dispersive solid-phase extraction combined with vortex-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet was developed for the determination of eight benzoylurea insecticides in soil and sewage sludge samples before high-performance liquid chromatography with ultraviolet detection. The analytes were first extracted from the soil and sludge samples into acetone under optimized pretreatment conditions. Clean-up of the extract was conducted by dispersive solid-phase extraction using activated carbon as the sorbent. The vortex-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet procedure was performed by using 1-undecanol with lower density than water as the extraction solvent, and the acetone contained in the solution also acted as dispersive solvent. Under the optimum conditions, the linearity of the method was in the range 2-500 ng/g with correlation coefficients (r) of 0.9993-0.9999. The limits of detection were in the range of 0.08-0.56 ng/g. The relative standard deviations varied from 2.16 to 6.26% (n = 5). The enrichment factors ranged from 104 to 118. The extraction recoveries ranged from 81.05 to 97.82% for all of the analytes. The good performance has demonstrated that the proposed methodology has a strong potential for application in the multiresidue analysis of complex matrices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Abiotic uptake of gases by organic soils

NASA Astrophysics Data System (ADS)

Smagin, A. V.

2007-12-01

Methodological and experimental studies of the abiotic uptake of gaseous substances by organic soils were performed. The static adsorption method of closed vessels for assessing the interaction of gases with the solid and liquid soil phases and the dynamic method of determining the sorption isotherms of gases by soils were analyzed. The theoretical substantiation of the methods and their practical implementations on the basis of a PGA-7 portable gas analyzer (Russia) were considered. Good agreement between the equilibrium sorption isotherms of the gases and the Langmuir model was revealed; for the real ranges of natural gas concentrations, this model can be reduced to the linear Henry equation. The limit values of the gas sorption (Langmuir monolayer capacity) are typical for dry samples; they vary from 670 4000 g/m3 for methane and oxygen to 20 000 25 000 g/m3 for carbon dioxide. The linear distribution coefficients of gases between the solid and gas phases of organic soils (Henry constants) are 8 18 units for poorly sorbed gases (O2, CH4) and 40 60 units for CO2. The kinetics of the chemicophysical uptake of gases by the soil studied is linear in character and obeys the relaxation kinetic model of the first order with the corresponding relaxation constants, which vary from 1 h -1 in wet samples to 10 h -1 in dry samples.

The importance of organic matter distribution and extract soil:solution ratio on the desorption of heavy metals from soils.

PubMed

Yin, Yujun; Impellitteri, Christopher A; You, Sun-Jae; Allen, Herbert E

2002-03-15

The lability (mobility and bioavailability) of metals varies significantly with soil properties for similar total soil metal concentrations. We studied desorption of Cu, Ni and Zn, from 15 diverse, unamended soils. These studies included evaluation of the effects of soil:solution extraction ratio and the roles of soil properties on metal desorption. Dcsorption was examined for each metal by computing distribution coefficients (Kd) for each metal in each soil where Kd = [M]soil/[M]solution, Results from soil:solution ratio studies demonstrated that Kd values for the metals tended to increase with increasing soil:solution ratio. This result also held true for distribution of soil organic matter (SOM). Because the soil:solution ratio has a significant effect on measured metal distributions, we selected a high soil:solution ratio to more closely approach natural soil conditions. Copper showed strong affinity to operationally defined dissolved organic matter (DOM). In this study, DOM was operationally defined based on the total organic carbon (TOC) content in 0.45-microm or 0.22-microm filtrates of the extracts. The Kd of Cu correlated linearly (r2 = 0.91) with the Kd of organic matter (Kd-om) where the Kd-om is equal to SOM as measured by Walkley-Black wet combustion and converted to total carbon (TC) by a factor of 0.59. These values representing solid phase TC were then divided by soluble organic carbon as measured by TOC analysis (DOM). The conversion factor of 0.59 was employed in order to construct Kd-om values based on solid phase carbon and solution phase carbon. SOM plays a significant role in the fate of Cu in soil systems. Soil-solution distribution of Ni and Zn, as well as the activity of free Cu2+, were closely related to SOM, but not to DOM. Kd values for Ni, Zn and free Cu2+ in a particular soil were divided by the SOM content in the same soil. This normalization of the Kd values for Ni, Zn, and free Cu2+ to the SOM content resulted in significant improvements in the linear relationships between non-normalized Kd values and soil pH. The semi-empirical normalized regression equations can be used to predict the solubility of Ni and Zn and the activity of free Cu2+ as a function of pH.

Method and apparatus for optimized sampling of volatilizable target substances

DOEpatents

Lindgren, Eric R.; Phelan, James M.

2004-10-12

An apparatus for capturing, from gases such as soil gas, target analytes. Target analytes may include emanations from explosive materials or from residues of explosive materials. The apparatus employs principles of sorption common to solid phase microextraction, and is best used in conjunction with analysis means such as a gas chromatograph. To sorb target analytes, the apparatus functions using various sorptive structures to capture target analyte. Depending upon the embodiment, those structures may include a capillary tube including an interior surface on which sorptive material (similar to that on the surface of a SPME fiber) is supported (along with means for moving gases through the capillary tube so that the gases come into close proximity to the sorptive material). In one disclosed embodiment, at least one such sorptive structure is associated with an enclosure including an opening in communication with the surface of a soil region potentially contaminated with buried explosive material such as unexploded ordnance. Emanations from explosive materials can pass into and accumulate in the enclosure where they are sorbed by the sorptive structures. Also disclosed is the use of heating means such as microwave horns to drive target analytes into the soil gas from solid and liquid phase components of the soil.

Ligandless surfactant mediated solid phase extraction combined with Fe₃O₄ nano-particle for the preconcentration and determination of cadmium and lead in water and soil samples followed by flame atomic absorption spectrometry: multivariate strategy.

PubMed

Jalbani, N; Soylak, M

2014-04-01

In the present study, a microextraction technique combining Fe3O4 nano-particle with surfactant mediated solid phase extraction ((SM-SPE)) was successfully developed for the preconcentration/separation of Cd(II) and Pb(II) in water and soil samples. The analytes were determined by flame atomic absorption spectrometry (FAAS). The effective variables such as the amount of adsorbent (NPs), the pH, concentration of non-ionic (TX-114) and centrifugation time (min) were investigated by Plackett-Burman (PBD) design. The important variables were further optimized by central composite design (CCD). Under the optimized conditions, the detection limits (LODs) of Cd(II) and Pb(II) were 0.15 and 0.74 µg/L, respectively. The validation of the proposed procedure was checked by the analysis of certified reference materials of TMDA 53.3 fortified water and GBW07425 soil. The method was successfully applied for the determination of Cd(II) and Pb(II) in water and soil samples. Copyright © 2014 Elsevier Inc. All rights reserved.

In situ measurement of solution concentrations and fluxes of sulfonamides and trimethoprim antibiotics in soils using o-DGT.

PubMed

Chen, Chang-Er; Chen, Wei; Ying, Guang-Guo; Jones, Kevin C; Zhang, Hao

2015-01-01

Techniques, such as Diffusive Gradients in Thin-films (DGT), which either minimally disturb the soil or perturb it in a controlled way are most likely to provide information relevant to toxicity. Herein, we report the first use of DGT for organics (o-DGT) in soil systems to gain insight into the mobility and lability of four antibiotics-sulfamethoxazole (SMX), sulfamethazine (SMZ), and sulfadimethoxine (SDM), trimethoprim (TMP) in soil. In experiments where the same known amount of antibiotics were spiked into the soil, which was then further modified with NaOH, NaCl or dissolved organic matter, directly measured soil solution concentrations (Csoln) of these antibiotics were in the order: SMX>SMZ≈SDM>TMP. The R values (ratio of concentrations measured by o-DGT and directly in solution) were 0.56, 0.41, 0.40 and 0.28, respectively, indicating that the removal of these antibiotics from the solution can be to some extent resupplied by release from the solid phase. The nonlinearity of the relationship between o-DGT fluxes and the reciprocal of diffusive layer thickness (Δg) also suggested that soil solution concentrations were only partially sustained by the solid phase. The potential fluxes of these antibiotics in this soil were 5.4, 3.6, 2.4, and 1.2 pg/cm(2)/s for SMX, SMZ, SDM, and TMP, respectively. o-DGT is a promising tool for understanding the fate and behaviour of polar organic chemicals in soil, and it potentially provides an in situ approach for assessing their bioavailability. Copyright © 2014 Elsevier B.V. All rights reserved.

Heating of solid earthen material, measuring moisture and resistivity

DOEpatents

Heath, William O.; Gauglitz, Phillip A.; Pillay, Gautam; Bergsman, Theresa M.; Eschbach, Eugene A.; Goheen, Steven C.; Richardson, Richard L.; Roberts, Janet S.; Schalla, Ronald

1996-01-01

The present invention includes a method of treating solid earthen material having volatile, semi-volatile, and non-volatile contaminants that utilizes electrical energy. A plurality of electrodes are inserted into a region of earthen material to be treated in a selected geometric pattern. Varying phase and voltages configurations are applied to corresponding electrodes to achieve heating, physical phase changes, and the placement of substances within the treatment region. Additionally, treatment mediums can be added to either treat the contamination within the soil or to restrict their mobility.

Heating of solid earthen material, measuring moisture and resistivity

DOEpatents

Heath, W.O.; Gauglitz, P.A.; Pillay, G.; Bergsman, T.M.; Eschbach, E.A.; Goheen, S.C.; Richardson, R.L.; Roberts, J.S.; Schalla, R.

1996-08-13

The present invention includes a method of treating solid earthen material having volatile, semi-volatile, and non-volatile contaminants that utilizes electrical energy. A plurality of electrodes are inserted into a region of earthen material to be treated in a selected geometric pattern. Varying phase and voltages configurations are applied to corresponding electrodes to achieve heating, physical phase changes, and the placement of substances within the treatment region. Additionally, treatment mediums can be added to either treat the contamination within the soil or to restrict their mobility. 29 figs.

Evaluation of multi-walled carbon nanotubes as solid-phase extraction adsorbents of pesticides from agricultural, ornamental and forestal soils.

PubMed

Asensio-Ramos, M; Hernández-Borges, J; Borges-Miquel, T M; Rodríguez-Delgado, M A

2009-08-11

A new, simple and cost-effective method based on the use of multi-walled carbon nanotubes (MWCNTs) as solid-phase extraction stationary phases is proposed for the determination of a group of seven organophosphorus pesticides (i.e. ethoprophos, diazinon, chlorpyriphos-methyl, fenitrothion, malathion, chlorpyriphos and phosmet) and one thiadiazine (buprofezin) in different kinds of soil samples (forestal, ornamental and agricultural) using gas chromatography with nitrogen phosphorus detection. Soils were first ultrasound extracted with 10 mL 1:1 methanol/acetonitrile (v/v) and the evaporated extract redissolved in 20 mL water (pH 6.0) was passed through 100 mg of MWCNTs of 10-15 nm o.d., 2-6 nm i.d. and 0.1-10 microm length. Elution was carried out with 20 mL dichloromethane. The method was validated in terms of linearity, precision, recovery, accuracy and selectivity. Matrix-matched calibration was carried out for each type of soil since statistical differences between the calibration curves constructed in pure solvent and in the reconstituted soil extract were found for most of the pesticides under study. Recovery values of spiked samples ranged between 54 and 91% for the three types of soils (limits of detection (LODs) between 2.97 and 9.49 ngg(-1)), except for chlorpyrifos, chlorpyrifos-methyl and buprofezin which ranged between 12 and 54% (LODs between 3.14 and 72.4 ngg(-1)), which are the pesticides with the highest soil organic carbon sorption coefficient (K(OC)) values. Using a one-sample test (Student's t-test) with fortified samples at two concentration levels in each type of soil, no significant differences were observed between the real and the experimental values (accuracy percentages ranged between 87 and 117%). It is the first time that the adsorptive potential of MWCNTs for the extraction of organophosphorus pesticides from soils is investigated.

Impacts of Activated Carbon Amendment on Hg Methylation, Demethylation and Microbial Activity in Marsh Soils

NASA Astrophysics Data System (ADS)

Gilmour, C. C.; Ghosh, U.; Santillan, E. F. U.; Soren, A.; Bell, J. T.; Butera, D.; McBurney, A. W.; Brown, S.; Henry, E.; Vlassopoulos, D.

2015-12-01

In-situ sorbent amendments are a low-impact approach for remediation of contaminants in sediments, particular in habitats like wetlands that provide important ecosystem services. Laboratory microcosm trials (Gilmour et al. 2013) and early field trials show that activated carbon (AC) can effectively increase partitioning of both inorganic Hg and methylmercury to the solid phase. Sediment-water partitioning can serve as a proxy for Hg and MeHg bioavailability in soils. One consideration in using AC in remediation is its potential impact on organisms. For mercury, a critical consideration is the potential impact on net MeHg accumulation and bioavailability. In this study, we specifically evaluated the impact of AC on rates of methylmercury production and degradation, and on overall microbial activity, in 4 different Hg-contaminated salt marsh soils. The study was done over 28 days in anaerobic, sulfate-reducing slurries. A double label of enriched mercury isotopes (Me199Hg and inorganic 201Hg) was used to separately follow de novo Me201Hg production and Me199Hg degradation. AC amendments decreased both methylation and demethylation rate constants relative to un-amended controls, but the impact on demethylation was stronger. The addition of 5% (dry weight) regenerated AC to soil slurries drove demethylation rate constants to nearly zero; i.e. MeHg sorption to AC almost totally blocked its degradation. The net impact was increased solid phase MeHg concentrations in some of the soil slurries with the highest methylation rate constants. However, the net impact of AC amendments was to increase MeHg (and inorganic Hg) partitioning to the soil phase and decrease concentrations in the aqueous phase. AC significantly decreased aqueous phase inorganic Hg and MeHg concentrations after 28 days. Overall, the efficacy of AC in reducing aqueous MeHg was highest in the soils with the highest MeHg concentrations. The AC addition did not significantly impact microbial activity, as assessed by CO2 production and sulfate depletion, in two of the four soils, but resulted in a up to a 40% decrease in two other soils. AC amendment has little effect on slurry pH, but decreased aqueous Fe, sulfide and DOC concentrations.

Extraction Techniques for Polycyclic Aromatic Hydrocarbons in Soils

PubMed Central

Lau, E. V.; Gan, S.; Ng, H. K.

2010-01-01

This paper aims to provide a review of the analytical extraction techniques for polycyclic aromatic hydrocarbons (PAHs) in soils. The extraction technologies described here include Soxhlet extraction, ultrasonic and mechanical agitation, accelerated solvent extraction, supercritical and subcritical fluid extraction, microwave-assisted extraction, solid phase extraction and microextraction, thermal desorption and flash pyrolysis, as well as fluidised-bed extraction. The influencing factors in the extraction of PAHs from soil such as temperature, type of solvent, soil moisture, and other soil characteristics are also discussed. The paper concludes with a review of the models used to describe the kinetics of PAH desorption from soils during solvent extraction. PMID:20396670

Micellar catalyzed degradation of fenitrothion, an organophosphorus pesticide, in solution and soils.

PubMed

Balakrishnan, Vimal K; Buncel, Erwin; Vanloon, Gary W

2005-08-01

We report on a study of the decomposition of fenitrothion (an organophosphorus pesticide that is a persistent contaminant in soils and groundwater) as catalyzed by cetyltrimethylammonium (CTA+) micelles. The CTA micelles were associated with two types of counterions: (1) inert counterions (e.g. CTABr) and (2) reactive counterions (e.g. CTAOH). The reactive counterion surfactants used were hydroxide anion (HO-) as a normal nucleophile and hydroperoxide anion (HOO-) and the anion of pyruvaldehyde oxime (MINA-) as two alpha-nucleophiles. The reactivity order followed: CTABr < CTAOH < CTAMINA < CTAOOH. Treatment of the rate data using the Pseudo-Phase Ion Exchange (PPIE) model of micellar catalysis showed the ratio k2M/k2w to be less than unity for all the surfactants employed. Rather than arising from a "true catalysis", we attributed the observed rate enhancements to a "concentration effect", where both pesticide and nucleophile were incorporated into the small micellar phase volume. Furthermore, the CTAOOH/CTAOH pair gave an alpha-effect of 57, showing that the alpha-effect can play an important role in micellar systems. We further investigated the effectiveness of reactive counterion surfactants in decontaminating selected environmental solids that were spiked with 27 ppb fenitrothion. The solids were as follows: the clay mineral montmorillonite and SO-1 and S0-2 soils (obtained from the Canadian Certified Reference Materials Project). The reactive counterion surfactant solutions significantly enhanced the rate of fenitrothion degradation in the spiked solids over that obtained when the spiked solid was placed in contact with either 0.02 M KOH or water. The rate enhancements followed the order CTAOOH > CTAMINA approximately CTAOH > KOH > water. We conclude that reactive counterion surfactants, especially with alpha-nucleophiles, hold great potential in terms of remediating soils contaminated by toxic organophosphorus esters.

Soil geochemical factors regulate Cd accumulation by metal hyperaccumulating Noccaea caerulescens (J. Presl & C. Presl) F.K. Mey in field-contaminated soils.

PubMed

Rosenfeld, Carla E; Chaney, Rufus L; Martínez, Carmen E

2018-03-01

Cadmium contamination in soil is a substantial global problem, and of significant concern due to high food-chain transfer. Cadmium hyperaccumulators are of particular interest because of their ability to tolerate and take up significant amounts of heavy metal pollution from soils. One particular plant, Noccaea caerulescens (formerly, Thlaspi caerulescens), has been extensively studied in terms of its capacity to accumulate heavy metals (specifically Zn and Cd), though these studies have primarily utilized hydroponic and metal-spiked model soil systems. We studied Cd and nutrient uptake by two N. caerulescens ecotypes, Prayon (Zn-only hyperaccumulator) and Ganges (Zn- and Cd-hyperaccumulator) in four long-term field-contaminated soils. Our data suggest that individual soil properties such as total soil Cd, Zn:Cd molar ratio, or soil pH do not accurately predict Cd uptake by hyperaccumulating plants. Additionally, total Cd uptake by the hyperaccumulating Ganges ecotype was substantially less than its physiological capacity, which is likely due to Cd-containing solid phases (primarily iron oxides) and pH that play an important role in regulating and limiting Cd solubility. Increased P accumulation in the Ganges leaves, and greater plant Fe accumulation from Cd-containing soils suggests that rhizosphere alterations via proton, and potentially organic acid, secretion may also play a role in nutrient and Cd acquisition by the plant roots. The current study highlights the role that soil geochemical factors play in influencing Cd uptake by hyperaccumulating plants. While these plants may have high physiological potential to accumulate metals from contaminated soils, individual soil geochemical factors and the plant-soil interactions in that soil will dictate the actual amount of phytoextractable metal. This underlines the need for site-specific understanding of metal-containing solid phases and geochemical properties of soils before undertaking phytoextraction efforts. Copyright © 2017 Elsevier B.V. All rights reserved.

Bioavailability and mobility of organic contaminants in soil: new three-step ecotoxicological evaluation.

PubMed

Prokop, Zbyněk; Nečasová, Anežka; Klánová, Jana; Čupr, Pavel

2016-03-01

A novel approach was developed for rapid assessment of bioavailability and potential mobility of contaminants in soil. The response of the same test organism to the organic extract, water extract and solid phase of soil was recorded and compared. This approach was designed to give an initial estimate of the total organic toxicity (response to organic extractable fraction), as well as the mobile (response to water extract) and bioavailable fraction (response to solid phase) of soil samples. Eighteen soil samples with different levels of pollution and content of organic carbon were selected to validate the novel three-step ecotoxicological evaluation approach. All samples were chemically analysed for priority contaminants, including aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), hexachlorocyclohexane (HCH) and dichlordiphenyltrichloroethane (DDT). The ecotoxicological evaluation involved determination of toxicity of the organic, mobile and bioavailable fractions of soil to the test organism, bacterium Bacillus cereus. We found a good correlation between the chemical analysis and the toxicity of organic extract. The low toxicity of water extracts indicated low water solubility, and thus, low potential mobility of toxic contaminants present in the soil samples. The toxicity of the bioavailable fraction was significantly greater than the toxicity of water-soluble (mobile) fraction of the contaminants as deduced from comparing untreated samples and water extracts. The bioavailability of the contaminants decreased with increasing concentrations of organic carbon in evaluated soil samples. In conclusion, the three-step ecotoxicological evaluation utilised in this study can give a quick insight into soil contamination in context with bioavailability and mobility of the contaminants present. This information can be useful for hazard identification and risk assessment of soil-associated contaminants. Graphical Abstract New three-step ecotoxicological evaluation by using the same organism.

Using the Image Analysis Method for Describing Soil Detachment by a Single Water Drop Impact

PubMed Central

Ryżak, Magdalena; Bieganowski, Andrzej

2012-01-01

The aim of the present work was to develop a method based on image analysis for describing soil detachment caused by the impact of a single water drop. The method consisted of recording tracks made by splashed particles on blotting paper under an optical microscope. The analysis facilitated division of the recorded particle tracks on the paper into drops, “comets” and single particles. Additionally, the following relationships were determined: (i) the distances of splash; (ii) the surface areas of splash tracks into relation to distance; (iii) the surface areas of the solid phase transported over a given distance; and (iv) the ratio of the solid phase to the splash track area in relation to distance. Furthermore, the proposed method allowed estimation of the weight of soil transported by a single water drop splash in relation to the distance of the water drop impact. It was concluded that the method of image analysis of splashed particles facilitated analysing the results at very low water drop energy and generated by single water drops.

Sorptive fractionation of organic matter and formation of organo-hydroxy-aluminum complexes during litter biodegradation in the presence of gibbsite

Treesearch

K. Heckman; A.S. Grandy; X. Gao; M. Keiluweit; K. Wickings; K. Carpenter; J. Chorover; C. Rasmussen

2013-01-01

Solid and aqueous phase Al species are recognized to affect organic matter (OM) stabilization in forest soils. However, little is known about the dynamics of formation, composition and dissolution of organo-Al hydroxide complexes in microbially-active soil systems, where plant litter is subject to microbial decomposition in close proximity to mineral weathering...

GRACE BIOREMEDIATION TECHNOLOGIES - DARAMEND™ BIOREMEDIATION TECHNOLOGY. INNOVATIVE TECHNOLOGY EVALUATION REPORT

EPA Science Inventory

Grace Dearborn's DARAMEND™ Bioremediation Technology was developed to treat soils/sediment contaminated with organic contaminants using solid-phase organic amendments. The amendments increase the soil’s ability to supply biologically available water/nutrients to micro...

Validation of material point method for soil fluidisation analysis

NASA Astrophysics Data System (ADS)

Bolognin, Marco; Martinelli, Mario; Bakker, Klaas J.; Jonkman, Sebastiaan N.

2017-06-01

The main aim of this paper is to describe and analyse the modelling of vertical column tests that undergo fluidisation by the application of a hydraulic gradient. A recent advancement of the material point method (MPM), allows studying both stationary and non-stationary fluid flow while interacting with the solid phase. The fluidisation initiation and post-fluidisation processes of the soil will be investigated with an advanced MPM formulation (Double Point) in which the behavior of the solid and the liquid phase is evaluated separately, assigning to each of them a set of material points (MPs). The result of these simulations are compared to analytic solutions and measurements from laboratory experiments. This work is used as a benchmark test for the MPM double point formulation in the Anura3D software and to verify the feasibility of the software for possible future engineering applications.

Unsteady numerical analysis of solid-liquid two-phase flow in stirred tank with double helical ribbon impeller

NASA Astrophysics Data System (ADS)

Bai, He; Chen, Xiangshan; Zhao, Guangyu; Xiao, Chenglei; Li, Chen; Zhong, Cheng; Chen, Yu

2017-08-01

In order to enhance the mixing process of soil contaminated by oil and water, one kind of double helical ribbon (DHR) impeller was developed. In this study, the unsteady simulation analysis of solid-liquid two-phase flow in stirring tank with DHR impeller was conducted by the the computational fluid dynamics and the multi-reference frame (MRF) method. It was found that at 0-3.0 s stage, the rate of liquid was greater than the rate of solid particles, while the power consumption was 5-6 times more than the smooth operation. The rates of the liquid and the solid particles were almost the same, and the required power was 32 KW at t > 3.0 s. The flow of the solid particles in the tank was a typical axial circle flow, and the dispersed sequence of the solid that was accumulated at the bottom of the tank was: the bottom loop region, the annular region near the wall of the groove and finally the area near axial center. The results show that the DHR impeller was suitable for the mixing of liquid-solid two-phase.

GEMAS: prediction of solid-solution phase partitioning coefficients (Kd) for oxoanions and boric acid in soils using mid-infrared diffuse reflectance spectroscopy.

PubMed

Janik, Leslie J; Forrester, Sean T; Soriano-Disla, José M; Kirby, Jason K; McLaughlin, Michael J; Reimann, Clemens

2015-02-01

The authors' aim was to develop rapid and inexpensive regression models for the prediction of partitioning coefficients (Kd), defined as the ratio of the total or surface-bound metal/metalloid concentration of the solid phase to the total concentration in the solution phase. Values of Kd were measured for boric acid (B[OH]3(0)) and selected added soluble oxoanions: molybdate (MoO4(2-)), antimonate (Sb[OH](6-)), selenate (SeO4(2-)), tellurate (TeO4(2-)) and vanadate (VO4(3-)). Models were developed using approximately 500 spectrally representative soils of the Geochemical Mapping of Agricultural Soils of Europe (GEMAS) program. These calibration soils represented the major properties of the entire 4813 soils of the GEMAS project. Multiple linear regression (MLR) from soil properties, partial least-squares regression (PLSR) using mid-infrared diffuse reflectance Fourier-transformed (DRIFT) spectra, and models using DRIFT spectra plus analytical pH values (DRIFT + pH), were compared with predicted log K(d + 1) values. Apart from selenate (R(2)  = 0.43), the DRIFT + pH calibrations resulted in marginally better models to predict log K(d + 1) values (R(2)  = 0.62-0.79), compared with those from PSLR-DRIFT (R(2)  = 0.61-0.72) and MLR (R(2)  = 0.54-0.79). The DRIFT + pH calibrations were applied to the prediction of log K(d + 1) values in the remaining 4313 soils. An example map of predicted log K(d + 1) values for added soluble MoO4(2-) in soils across Europe is presented. The DRIFT + pH PLSR models provided a rapid and inexpensive tool to assess the risk of mobility and potential availability of boric acid and selected oxoanions in European soils. For these models to be used in the prediction of log K(d + 1) values in soils globally, additional research will be needed to determine if soil variability is accounted on the calibration. © 2014 SETAC.

Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques

NASA Astrophysics Data System (ADS)

Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine

2016-04-01

Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg-1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike -Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L-1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not yet been applied to estimate the labile pool of mercury in contaminated soils. We performed a series of soil incubations spiked with 196Hg2+aiming at measuring and modelling the progressive assimilation of Hg ions into less labile forms. Soils with a wide range of characteristics are taken for our research purpose, inclusive of Hg concentrations ranging from 0.1 to 390 mg kg-1, pH between 3.5 - 7.5 and total organic carbon (TOC) between 2.5 - 8 %. In parallel, the labile pool of Hg estimated using ID will be compared with that determined using conventional extraction methods, e.g. sequential extraction procedures. These altogether allows us to answer (1) how the E-value of Hg in soils is comparable to those estimated based on selective extraction methods, (2) how the labile Hg correlates with the total soil Hg, soil pH and TOC, and (3) how the solubility of added Hg (e.g. via rainfall) decreased in soils of different properties during aging. The obtained results fills the knowledge gap concerning Hg biogeochemistry in the terrestrial environment and serves as a basis for estimating (and predicting) the risk of soil Hg diffusion from a point source to the adjacent environments.

Gas/solid particulate phthalic esters (PAEs) in Masson pine (Pinus massoniana L.) needles and rhizosphere surface soils.

PubMed

Wang, Wen-xin; Fan, Chinbay Q

2014-07-15

Phthalic acid esters (PAEs) are used in many branches of industry and are produced in huge amounts throughout the world. An investigation on particulate- and gas-phase distribution of PAEs has been conducted between January 2011 and December 2012 in Nanjing (China). Masson pine (Pinus massoniana L.) needles and rhizosphere surface soils were sampled from urban to suburban/remote sites, to investigate the pine needle/soil distribution of PAEs. The results showed that the average total PAE concentration (gas+particle) was 97.0ngm(-3). The six PAE congeners considered predominantly existed in the gas phase and the average contribution of gas phase to total PAEs ranged from 75.0% to 89.1%. The PAE concentrations in rhizosphere soils and pine needles were positively correlated with their particulate- and gas-phase concentrations, respectively, which suggested that surface soils accumulated PAEs mainly through gravity deposition of particles and pine needle stomata absorbed PAEs mainly from the gas phase. The gas/particle partitioning (KP) and soil-pine needle ratio (Rs/n) were determined. Experimentally determined KP values correlated well with the subcooled liquid vapor pressures (PL). A set of interesting relationships of logRs/n-logKP-logPL was employed to explain the experimental findings of PAEs deposition to surface soils and to needles. This data set offered a unique perspective into the influence that Rs/n played in KP and correlated with PL. Copyright © 2014 Elsevier B.V. All rights reserved.

Double-disk solid-phase extraction--Simultaneous cleanup and trace enrichment of herbicides and metabolites from environmental samples

USGS Publications Warehouse

Ferrar, Imma; Barceló, Damià; Thurman, E.M.

1999-01-01

Phenylurea and triazine herbicides, including some metabolites, were isolated from water and soil extracts by solid-phase extraction using a layered system of two extraction disks, a method called double-disk solid-phase extraction. The first disk consisted of strong anion exchange (SAX) of 10-μm styrene divinylbenzene (SDB) particles embedded in Teflon, and the second disk was a C18 disk of 10-μm particles also embedded in Teflon. A volume of 500 mL of water or aqueous soil extract is passed through the layered system with the SAX disk first. The purpose of the SAX disk is to remove the humic and fulvic acids from the water or aqueous soil extract by ion exchange through their carboxyl groups. Even during methanol elution of herbicides, the humic substances remain bound to the SAX disk with >85% retention. Elution with methanol results in more than 90% recovery of the herbicides from the layered extraction disks. Removal of the humic and fulvic acids results in greater sensitivity for diode array detection quantitation (0.05 μg/L for herbicides) by substantially reducing the absorbance of the humic peak on the LC chromatogram. The herbicides adsorb to the SAX disk either through hydrogen bonding to the anion-exchange sites or by hydrophobic interaction with the SDB surface of the anion-exchange disk. The method was tested for the analysis of natural water samples from the Mississippi Embayment, a cotton-growing area of the southeastern United States.

Modeling particle-facilitated solute transport using the C-Ride module of HYDRUS

NASA Astrophysics Data System (ADS)

Simunek, Jiri; Bradford, Scott A.

2017-04-01

Strongly sorbing chemicals (e.g., heavy metals, radionuclides, pharmaceuticals, and/or explosives) in soils are associated predominantly with the solid phase, which is commonly assumed to be stationary. However, recent field- and laboratory-scale observations have shown that, in the presence of mobile colloidal particles (e.g., microbes, humic substances, clays and metal oxides), the colloids could act as pollutant carriers and thus provide a rapid transport pathway for strongly sorbing contaminants. Such transport can be further accelerated since these colloidal particles may travel through interconnected larger pores where the water velocity is relatively high. Additionally, colloidal particles have a considerable adsorption capacity for other species present in water because of their large specific surface areas and their high concentrations in soil-water and groundwater. As a result, the transport of contaminants can be significantly, sometimes dramatically, enhanced when they are adsorbed to mobile colloids. To address this problem, we have developed the C-Ride module for HYDRUS-1D. This one-dimensional numerical module is based on the HYDRUS-1D software package and incorporates mechanisms associated with colloid and colloid-facilitated solute transport in variably saturated porous media. This numerical model accounts for both colloid and solute movement due to convection, diffusion, and dispersion in variably-saturated soils, as well as for solute movement facilitated by colloid transport. The colloids transport module additionally considers processes of attachment/detachment to/from the solid phase, straining, and/or size exclusion. Various blocking and depth dependent functions can be used to modify the attachment and straining coefficients. The module additionally considers the effects of changes in the water content on colloid/bacteria transport and attachment/detachment to/from solid-water and air-water interfaces. For example, when the air-water interface disappears during imbibition, particles residing on this interface are released into the liquid phase. Similarly, during drainage, particles residing at the solid-water interface may be detached from this interface by capillary forces and released into the liquid phase or become attached to the air-water interface. The solute transport module uses the concept of two-site sorption to describe nonequilibrium adsorption-desorption reactions to the solid phase. The module further assumes that the contaminant can be sorbed onto surfaces of both deposited and mobile colloids, fully accounting for the dynamics of colloids movement between different phases. We will demonstrate the use of the module using selected datasets and numerical examples.

Evidence for Different Reaction Pathways for Liquid and Granular Micronutrients in a Calcareous Soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hettiarachchi, Ganga M.; McLaughlin, Mike J.; Scheckel, Kirk G.

2008-06-16

The benefits of Mn and Zn fluid fertilizers over conventional granular products in calcareous sandy loam soils have been agronomically demonstrated. We hypothesized that the differences in the effectiveness between granular and fluid Mn and Zn fertilizers is due to different Mn and Zn reaction processes in and around fertilizer granules and fluid fertilizer bands. We used a combination of several synchrotron-based x-ray techniques, namely, spatially resolved micro-x-ray fluorescence (?-XRF), micro-x-ray absorption near edge structure spectroscopy (?-XANES), and bulk-XANES and -extended x-ray absorption fine structure (EXAFS) spectroscopy, along with several laboratory-based x-ray techniques to speciate different fertilizer-derived Mn and Znmore » species in highly calcareous soils to understand the chemistry underlying the observed differential behavior of fluid and granular micronutrient forms. Micro-XRF mapping of soil-fertilizer reactions zones indicated that the mobility of Mn and Zn from liquid fertilizer was greater than that observed for equivalent granular sources of these micronutrients in soil. After application of these micronutrient fertilizers to soil, Mn and Zn from liquid fertilizers were found to remain in comparatively more soluble solid forms, such as hydrated Mn phosphate-like, Mn calcite-like, adsorbed Zn-like, and Zn silicate-like phases, whereas Mn and Zn from equivalent granular sources tended to transform into comparatively less soluble solid forms such as Mn oxide-like, Mn carbonate-like, and Zn phosphate-like phases.« less

Simultaneous quantification of Aroclor mixtures in soil samples by gas chromatography/mass spectrometry with solid phase microextraction using partial least-squares regression.

PubMed

Zhang, Mengliang; Harrington, Peter de B

2015-01-01

Multivariate partial least-squares (PLS) method was applied to the quantification of two complex polychlorinated biphenyls (PCBs) commercial mixtures, Aroclor 1254 and 1260, in a soil matrix. PCBs in soil samples were extracted by headspace solid phase microextraction (SPME) and determined by gas chromatography/mass spectrometry (GC/MS). Decachlorinated biphenyl (deca-CB) was used as internal standard. After the baseline correction was applied, four data representations including extracted ion chromatograms (EIC) for Aroclor 1254, EIC for Aroclor 1260, EIC for both Aroclors and two-way data sets were constructed for PLS-1 and PLS-2 calibrations and evaluated with respect to quantitative prediction accuracy. The PLS model was optimized with respect to the number of latent variables using cross validation of the calibration data set. The validation of the method was performed with certified soil samples and real field soil samples and the predicted concentrations for both Aroclors using EIC data sets agreed with the certified values. The linear range of the method was from 10μgkg(-1) to 1000μgkg(-1) for both Aroclor 1254 and 1260 in soil matrices and the detection limit was 4μgkg(-1) for Aroclor 1254 and 6μgkg(-1) for Aroclor 1260. This holistic approach for the determination of mixtures of complex samples has broad application to environmental forensics and modeling. Copyright © 2014 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weaver, G.T.; Kanna, P.K.; Beese, F.

A shallow slightly acid Terra fusca (Rendolls) soil derived from triassic limestone contains substantial amounts of sulfate. Under high sulfate input, low pH and high salt input this soil can further retain sulfate. Soil chemical data indicate that this soil contains exchangeable Al and H. This finding and the analysis of the equilibrium soil solutions from batch and percolation studies indicate that the retention of sulfate can be described by an equilibrium solid/solution phase of the type Al(OH)SO4 (aluminum hydroxy sulfate). Under similar experimental conditions of solution composition and concentration, Freundlich type adsorption/desorption isotherms and the general solute transport equationmore » can describe the retention and transport of sulfate in this soil.« less

Survey monitoring results on the reduction of micropollutants, bacteria, bacteriophages and TSS in retention soil filters.

PubMed

Tondera, Katharina; Koenen, Stefan; Pinnekamp, Johannes

2013-01-01

A main source of surface water pollution in Western Europe stems from combined sewer overflow. One of the few technologies available to reduce this pollution is the retention soil filter. In this research project, we evaluated the cleaning efficiency of retention soil filters measuring the concentration ratio of standard wastewater parameters and bacteria according to factors limiting efficiency, such as long dry phases or phases of long-lasting retention. Furthermore, we conducted an initial investigation on how well retention soil filters reduce certain micropollutants on large-scale plants. There was little precipitation during the 1-year sampling phase, which led to fewer samples than expected. Nevertheless, we could verify how efficiently retention soil filters clean total suspended solids. Our results show that retention soil filters are not only able to eliminate bacteria, but also to retain some of the micropollutants investigated here. As the filters were able to reduce diclofenac, bisphenol A and metoprolol by a median rate of almost 75%, we think that further investigations should be made into the reduction processes in the filter. At this point, a higher accuracy in the results could be achieved by conducting bench-scale experiments.

Temperature dependence and coupling of iron and arsenic reduction and release during flooding of a contaminated soil.

PubMed

Weber, Frank-Andreas; Hofacker, Anke F; Voegelin, Andreas; Kretzschmar, Ruben

2010-01-01

Arsenic (As) in soils and sediments is commonly mobilized when anoxic conditions promote microbial iron (Fe) and As reduction. Recent laboratory studies and field observations have suggested a decoupling between Fe and As reduction and release, but the links between these processes are still not well understood. In microcosm experiments, we monitored the formation of Fe(II) and As(III) in the porewater and in the soil solid-phase during flooding of a contaminated floodplain soil at temperatures of 23, 14, and 5 degrees C. At all temperatures, flooding induced the development of anoxic conditions and caused increasing concentrations of dissolved Fe(II) and As(III). Decreasing the temperature from 23 to 14 and 5 degrees C strongly slowed down soil reduction and Fe and As release. Speciation of As in the soil solid-phase by X-ray absorption spectroscopy (XAS) and extraction of the Fe(II) that has formed by reductive Fe(III) (hydr)oxide dissolution revealed that less than 3.9% of all As(III) and less than 3.2% of all Fe(II) formed during 52 days of flooding at 23 degrees C were released into the porewater, although 91% of the initially ascorbate-extractable Fe and 66% of the total As were reduced. The amount of total As(III) formed during soil reduction was linearly correlated to the amount of total Fe(II) formed, indicating that the rate of As(V) reduction was controlled by the rate of microbial Fe(III) (hydr)oxide reduction.

Determination of 13 endocrine disrupting chemicals in environmental solid samples using microwave-assisted solvent extraction and continuous solid-phase extraction followed by gas chromatography-mass spectrometry.

PubMed

Azzouz, Abdelmonaim; Ballesteros, Evaristo

2016-01-01

Soil can contain large numbers of endocrine disrupting chemicals (EDCs). The varied physicochemical properties of EDCs constitute a great challenge to their determination in this type of environmental matrix. In this work, an analytical method was developed for the simultaneous determination of various classes of EDCs, including parabens, alkylphenols, phenylphenols, bisphenol A, and triclosan, in soils, sediments, and sewage sludge. The method uses microwave-assisted extraction (MAE) in combination with continuous solid-phase extraction for determination by gas chromatography-mass spectrometry. A systematic comparison of the MAE results with those of ultrasound-assisted and Soxhlet extraction showed MAE to provide the highest extraction efficiency (close to 100%) in the shortest extraction time (3 min). The proposed method provides a linear response over the range 2.0 - 5000 ng kg(-1) and features limits of detection from 0.5 to 4.5 ng kg(-1) depending on the properties of the EDC. The method was successfully applied to the determination of target compounds in agricultural soils, pond and river sediments, and sewage sludge. The sewage sludge samples were found to contain all target compounds except benzylparaben at concentration levels from 36 to 164 ng kg(-1). By contrast, the other types of samples contained fewer EDCs and at lower concentrations (5.6 - 84 ng kg(-1)).

Evaluating specificity of sequential extraction for chemical forms of lead in artificially-contaminated and field-contaminated soils.

PubMed

Tai, Yiping; McBride, Murray B; Li, Zhian

2013-03-30

In the present study, we evaluated a commonly employed modified Bureau Communautaire de Référence (BCR test) 3-step sequential extraction procedure for its ability to distinguish forms of solid-phase Pb in soils with different sources and histories of contamination. When the modified BCR test was applied to mineral soils spiked with three forms of Pb (pyromorphite, hydrocerussite and nitrate salt), the added Pb was highly susceptible to dissolution in the operationally-defined "reducible" or "oxide" fraction regardless of form. When three different materials (mineral soil, organic soil and goethite) were spiked with soluble Pb nitrate, the BCR sequential extraction profiles revealed that soil organic matter was capable of retaining Pb in more stable and acid-resistant forms than silicate clay minerals or goethite. However, the BCR sequential extraction for field-collected soils with known and different sources of Pb contamination was not sufficiently discriminatory in the dissolution of soil Pb phases to allow soil Pb forms to be "fingerprinted" by this method. It is concluded that standard sequential extraction procedures are probably not very useful in predicting lability and bioavailability of Pb in contaminated soils. Copyright © 2013 Elsevier B.V. All rights reserved.

RCRA facility investigation and risk assessment, McAlester Army Ammunition Plant, McAlester, Oklahoma. Supplemental phase 2 RFI report, Solid Waste Management Units 32 and 33

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1994-11-30

This report presents the results of the Supplemental Phase 2 Resource Conservation and Recovery Act (RCRA) Facility Investigation (RFI) conducted for Solid Waste Management Units (SWMU) Number 32 and Number 33 at McAlester Army Ammunition Plant (MCAAP). The supplemental action of the RFI was conducted as part of the actions required in connection with the application for a RCRA permit for the management of hazardous waste at MCAAP. The objective of this Supplemental Phase 2 RFI is to collect and analyze soil samples from Solid Waste Management Unit (SWMU) 32 and SWMU 33 for dioxins/dibenzofurans. The purpose of this reportmore » is to describe the procedures used to perform the Supplemental Phase 2 RFI to present and assess the results obtained in terms of the nature and extent of any contamination found, to present the results of human health and ecological risk assessments, and to recommend future actions.« less

Nickel speciation in several serpentine (ultramafic) topsoils via bulk synchrotron-based techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siebecker, Matthew G.; Chaney, Rufus L.; Sparks, Donald L.

2017-07-01

Serpentine soils have elevated concentrations of trace metals including nickel, cobalt, and chromium compared to non-serpentine soils. Identifying the nickel bearing minerals allows for prediction of potential mobility of nickel. Synchrotron-based techniques can identify the solid-phase chemical forms of nickel with minimal sample treatment. Element concentrations are known to vary among soil particle sizes in serpentine soils. Sonication is a useful method to physically disperse sand, silt and clay particles in soils. Synchrotron-based techniques and sonication were employed to identify nickel species in discrete particle size fractions in several serpentine (ultramafic) topsoils to better understand solid-phase nickel geochemistry. Nickel commonlymore » resided in primary serpentine parent material such as layered-phyllosilicate and chain-inosilicate minerals and was associated with iron oxides. In the clay fractions, nickel was associated with iron oxides and primary serpentine minerals, such as lizardite. Linear combination fitting (LCF) was used to characterize nickel species. Total metal concentration did not correlate with nickel speciation and is not an indicator of the major nickel species in the soil. Differences in soil texture were related to different nickel speciation for several particle size fractionated samples. A discussion on LCF illustrates the importance of choosing standards based not only on statistical methods such as Target Transformation but also on sample mineralogy and particle size. Results from the F-test (Hamilton test), which is an underutilized tool in the literature for LCF in soils, highlight its usefulness to determine the appropriate number of standards to for LCF. EXAFS shell fitting illustrates that destructive interference commonly found for light and heavy elements in layered double hydroxides and in phyllosilicates also can occur in inosilicate minerals, causing similar structural features and leading to false positive results in LCF.« less

Nutrient variations from swine manure to agricultural land

PubMed Central

You, Byung-Gu; Shim, Soomin; Choi, Yoon-Seok

2018-01-01

Objective Swine manure in Korea is separated into solid and liquid phases which are composted separately and then applied on land. The nutrient accumulation in soil has been a big issue in Korea but the basic investigation about nutrient input on arable land has not been achieved in detail. Within the nutrient production from livestock at the national level, most values are calculated by multiplication of the number of animals with the excreta unit per animal. However, the actual amount of nutrients from swine manure may be totally different with the nutrients applied to soil since livestock breeding systems are not the same with each country. Methods This study investigated 15 farms producing solid compost and 14 farms producing liquid compost. Composting for solid phase used the Turning+Aeration (TA) or Turning (T) only methods, while liquid phase aeration composting was achieved by continuous (CA), intermittent (IA), or no aeration (NA). Three scenarios were constructed for investigating solid compost: i) farm investigation, ii) reference study, and iii) theoretical P changes (ΔP = 0), whereas an experiment for water evaporation was conducted for analyzing liquid compost. Results In farm investigation, weight loss rates of 62% and 63% were obtained for TA and T, respectively, while evaporation rates for liquid compost were 8.75, 7.27, and 5.14 L/m2·d for CA, IA, and NA, respectively. Farm investigation provided with the combined nutrient load (solid+liquid) of VS, N, and P of 117.6, 7.2, and 2.7 kg/head·yr. Nutrient load calculated from farm investigation is about two times higher than the calculated with reference documents. Conclusion The nutrient loading coefficients from one swine (solid+liquid) were (volatile solids, 0.79; nitrogen, 0.53; phosphorus, 0.71) with nutrient loss of 21%, 47%, and 29%, respectively. The nutrient count from livestock manure using the excretion unit has probably been overestimated without consideration of the nutrient loss. PMID:29268574

Role of root exudates in dissolution of Cd containing iron oxides

NASA Astrophysics Data System (ADS)

Rosenfeld, C.; Martinez, C. E.

2011-12-01

Dissolved organic matter (DOM) in the rhizosphere contains organic acids, amino acids and more complex organic molecules that can substantially impact the solubility of soil solid phases. Plant roots and soil microorganisms contribute a large fraction of these organic compounds to DOM, potentially accelerating the transfer of solid phase elements into solution. In highly contaminated soils, heavy metals such as Cd are commonly found coprecipitated with common minerals (e.g. iron oxides). Introducing or changing vegetation on these contaminated soils may increase DOM levels in the soil pore fluids and thus enhance the biological and chemical weathering of soil minerals. Here, we investigate the role of root exudates on mineral dissolution and Cd mobility in contaminated soils. We hypothesize that plant exudates containing nitrogen and sulfur functional groups will dissolve Cd-containing mineral phases to a greater extent than exudates containing only oxygen functional groups, resulting in higher Cd concentrations in solution. Two different iron oxide mineral phases were utilized in a laboratory-scale model study system investigating the effects of low molecular weight, oxygen-, nitrogen-, and sulfur-containing organic compounds on mineral dissolution. Goethite (α-FeOOH) was synthesized in the laboratory with 0, 2.4, 5, and 100 theoretical mol% Cd, and franklinite (ZnFe2O4) was prepared with 0, 10, and 25 theoretical mol% Cd. Phase identity of all minerals was verified with X-ray diffraction (XRD). All minerals were reacted with 0.01 mM solutions containing one of four different organic ligands (oxalic acid, citric acid, histidine or cysteine) and aliquots of these solutions were sampled periodically over 40 days. Results from solution samples suggest that oxalic acid, citric acid, and histidine consistently increase mineral dissolution relative to the control (no organic compound present) while cysteine consistently inhibits dissolution relative to the control in all minerals. Increasing Cd substitution in the franklinite resulted in increased release of Fe and Zn to solution in the presence of these organic compounds, while increasing Cd substitution in the goethite generally limited Fe release to solution. In the case of cysteine, sulfur concentrations in solution decrease over time in the presence of Cd-containing minerals, indicating strong binding of the cysteine compound to the mineral surface, inhibiting Cd dissolution from the minerals. Our work indicates that amino acids present in biological soil exudates, in addition to organic acids, may have substantial impacts on iron oxide dissolution in soils, altering the availability of both bioessential (e.g., Fe and Zn) and non-essential, or potentially toxic, (e.g., Cd) elements.

Laundry Detergency of Solid Non-Particulate Soil Using Microemulsion-Based Formulation.

PubMed

Chanwattanakit, Jarussri; Chavadej, Sumaeth

2018-02-01

Laundry detergency of solid non-particulate soil on polyester and cotton was investigated using a microemulsion-based formulation, consisting of an anionic extended surfactant (C 12,13 -4PO-SO 4 Na) and sodium mono-and di-methyl naphthalene sulfonate (SMDNS) as the hydrophilic linker, to provide a Winsor Type III microemulsion with an ultralow interfacial tension (IFT). In this work, methyl palmitate (palmitic acid methyl ester) having a melting point around 30°C, was used as a model solid non-particulate (waxy) soil. A total surfactant concentration of 0.35 wt% of the selected formulation (4:0.65 weight ratio of C 12,13 -4PO-SO 4 Na:SMDNS) with 5.3 wt% NaCl was able to form a middle phase microemulsion at a high temperature (40°C),which provided the highest oil removal level with the lowest oil redeposition and the lowest IFT, and was much higher than that with a commercial detergent or de-ionized water. Most of the detached oil, whether in liquid or solid state, was in an unsolubilized form. Hence, the dispersion stability of the detached oil droplets or solidified oil particles that resulted from the surfactant adsorption played an important role in the oil redeposition. For an oily detergency, the lower the system IFT, the higher the oil removal whereas for a waxy (non-particulate) soil detergency, the lower the contact angle, the higher the solidified oil removal. For a liquefied oil, the detergency mechanism was roll up and emulsification with dispersion stability, while that for the waxy soil (solid oil) was the detachment by wettability with dispersion stability.

Comparative characterization of sewage sludge compost and soil: Heavy metal leaching characteristics.

PubMed

Fang, Wen; Wei, Yonghong; Liu, Jianguo

2016-06-05

The leaching and accumulation of heavy metals are major concerns following the land application of sewage sludge compost (SSC). We comparatively characterized SSC, the reference soil, and the SSC amended soil to investigate their similarities and differences regarding heavy metal leaching behavior and then to evaluate the effect of SSC land application on the leaching behavior of soil. Results showed that organic matter, including both of particulate organic matter (POM) and dissolved organic matter (DOM), were critical factors influencing heavy metal leaching from both of SSC and the soil. When SSC was applied to soil at the application rate of 48t/ha, the increase of DOM content slightly enhanced heavy metal leaching from the amended soil over the applicable pH domain (6

Effects of soil tillage on the microwave emission of soils

NASA Technical Reports Server (NTRS)

Jackson, T. J.; Koopman, G. J.; Oneill, P. E.; Wang, J. R.

1985-01-01

In order to understand the interactions of soil properties and microwave emission better, a series of field experiments were conducted in 1984. Small plots were measured with a truck-mounted passive microwave radiometer operating at 1.4 GHz. These data were collected concurrent with ground observations of soil moisture and bulk density. Treatment effects studied included different soil moisture contents and bulk densities. Evaluations of the data have shown that commonly used models of the dielectric properties of wet soils do not explain the observations obtained in these experiments. This conclusion was based on the fact that the roughness parameters determined through optimization were significantly larger than those observed in similar investigations. These discrepancies are most likely due to the soil structure. Commonly used models assume a homogeneous three phase mixture of soil solids, air and water. Under tilled conditions the soil is actually a two phase mixture of aggregates and voids. Appropriate dielectric models for this tilled condition were evaluated and found to explain the observations. These results indicate that previous conclusions concerning the effects of surface roughness in tilled fields may be incorrect, and they may explain some of the inconsistencies encountered in roughness modeling.

The two-phase flow IPTT method for measurement of nonwetting-wetting liquid interfacial areas at higher nonwetting saturations in natural porous media

PubMed Central

Zhong, Hua; Ouni, Asma El; Lin, Dan; Wang, Bingguo; Brusseau, Mark L

2017-01-01

Interfacial areas between nonwetting-wetting (NW-W) liquids in natural porous media were measured using a modified version of the interfacial partitioning tracer test (IPTT) method that employed simultaneous two-phase flow conditions, which allowed measurement at NW saturations higher than trapped residual saturation. Measurements were conducted over a range of saturations for a well-sorted quartz sand under three wetting scenarios of primary drainage (PD), secondary imbibition (SI), and secondary drainage (SD). Limited sets of experiments were also conducted for a model glass-bead medium and for a soil. The measured interfacial areas were compared to interfacial areas measured using the standard IPTT method for liquid-liquid systems, which employs residual NW saturations. In addition, the theoretical maximum interfacial areas estimated from the measured data are compared to specific solid surface areas measured with the N2/BET method and estimated based on geometrical calculations for smooth spheres. Interfacial areas increase linearly with decreasing water saturation over the range of saturations employed. The maximum interfacial areas determined for the glass beads, which have no surface roughness, are 32±4 and 36±5 cm−1 for PD and SI cycles, respectively. The values are similar to the geometric specific solid surface area (31±2 cm−1) and the N2/BET solid surface area (28±2 cm−1). The maximum interfacial areas are 274±38, 235±27, and 581±160 cm−1 for the sand for PD, SI, and SD cycles, respectively, and ~7625 cm−1 for the soil for PD and SI. The maximum interfacial areas for the sand and soil are significantly larger than the estimated smooth-sphere specific solid surface areas (107±8 cm−1 and 152±8 cm−1, respectively), but much smaller than the N2/BET solid surface area (1387±92 cm−1 and 55224 cm−1, respectively). The NW-W interfacial areas measured with the two-phase flow method compare well to values measured using the standard IPTT method. PMID:28959079

Poroelastic theory of consolidation in unsaturated soils incorporating gravitational body forces

NASA Astrophysics Data System (ADS)

Lo, Wei-Cheng; Chao, Nan-Chieh; Chen, Chu-Hui; Lee, Jhe-Wei

2017-08-01

The generalization of the poroelasticity theory of consolidation in unsaturated soils to well represent gravitational body forces is presented in the current study. Three partial differential equations featuring the displacement vector of the solid phase, along with the excess pore water and air pressures as dependent variables are derived, with coupling that occurs in the first-order temporal- and spatial- derivative terms. The former arises from viscous drag between solid and fluid, whereas the latter is attributed to the presence of gravity. Given the physically-consistent initial and boundary conditions, these coupled equations are numerically solved under uniaxial strain as a representative example. Our results reveal that variations in the excess pore water pressure due to the existence of gravitational forces increase with soil depth, but these variations are not significant if the soil layer is not sufficiently long. A dimensionless parameter is defined theoretically to quantify the impact of those forces on the final total settlement. This impact is shown to become greater as the soil layer is less stiff and has more length, and bears an inversely-proportional trend with initial water saturation.

A SPH elastic-viscoplastic model for granular flows and bed-load transport

NASA Astrophysics Data System (ADS)

Ghaïtanellis, Alex; Violeau, Damien; Ferrand, Martin; Abderrezzak, Kamal El Kadi; Leroy, Agnès; Joly, Antoine

2018-01-01

An elastic-viscoplastic model (Ulrich, 2013) is combined to a multi-phase SPH formulation (Hu and Adams, 2006; Ghaitanellis et al., 2015) to model granular flows and non-cohesive sediment transport. The soil is treated as a continuum exhibiting a viscoplastic behaviour. Thus, below a critical shear stress (i.e. the yield stress), the soil is assumed to behave as an isotropic linear-elastic solid. When the yield stress is exceeded, the soil flows and behaves as a shear-thinning fluid. A liquid-solid transition threshold based on the granular material properties is proposed, so as to make the model free of numerical parameter. The yield stress is obtained from Drucker-Prager criterion that requires an accurate computation of the effective stress in the soil. A novel method is proposed to compute the effective stress in SPH, solving a Laplace equation. The model is applied to a two-dimensional soil collapse (Bui et al., 2008) and a dam break over mobile beds (Spinewine and Zech, 2007). Results are compared with experimental data and a good agreement is obtained.

Solid phase microextraction field kit

DOEpatents

Nunes, Peter J.; Andresen, Brian D.

2005-08-16

A field kit for the collection, isolation and concentration of trace amounts of high explosives (HE), biological weapons (BW) and chemical weapons (CW) residues in air, soil, vegetation, swipe, and liquid samples. The field kit includes a number of Solid Phase Microextraction (SPME) fiber and syringe assemblies in a hermetically sealed transportation container or tubes which includes a sampling port, a number of extra SPME fiber and syringe assemblies, the fiber and syringe assemblies including a protective cap for the fiber, and an extractor for the protective cap, along with other items including spare parts, protective glove, and an instruction manual, all located in an airtight container.

Vapor-phase interactions and diffusion of organic solvents in the unsaturated zone

USGS Publications Warehouse

Roy, W.R.; Griffin, R.A.

1990-01-01

This article presents an analysis of the interactions and static movement of 37 organic solvents as vapors through the unsaturated soil zone. The physicochemical interactions of the organic vapors with unsaturated soil materials were emphasized with focus on diffusive, and adsorptive interactions. Fick's Law and porous media diffusion coefficients for most of the solvent vapors were either compiled or estimated; coefficients were not available for some of the fluorinated solvents. The adsorption of some of the solvent vapors by silica was concluded to be due to hydrogen bond formation with surface silanol groups. Heats of adsorption data for different adsorbents were also compiled. There were very few data on the adsorption of these solvent vapors by soils, but it appears that the magnitude of adsorption of nonpolar solvents is reduced as the relative humidity of the vapor-solid system is increased. Consequently, the interaction of the vapors may then separated into two processes; (1) gas-water partitioning described by Henry's Law constants, and (2) solid-water adsorption coefficients which may be estimated from liquid-solid partition coefficients (Kd values). ?? 1990 Springer-Verlag New York Inc.

High-throughput multipesticides residue analysis in earthworms by the improvement of purification method: Development and application of magnetic Fe3 O4 -SiO2 nanoparticles based dispersive solid-phase extraction.

PubMed

Sun, Yuhan; Qi, Peipei; Cang, Tao; Wang, Zhiwei; Wang, Xiangyun; Yang, Xuewei; Wang, Lidong; Xu, Xiahong; Wang, Qiang; Wang, Xinquan; Zhao, Changshan

2018-06-01

As a key representative organism, earthworms can directly illustrate the influence of pesticides on environmental organisms in soil ecosystems. The present work aimed to develop a high-throughput multipesticides residue analytical method for earthworms using solid-liquid extraction with acetonitrile as the solvent and magnetic material-based dispersive solid-phase extraction for purification. Magnetic Fe 3 O 4 nanoparticles were modified with a thin silica layer to form Fe 3 O 4 -SiO 2 nanoparticles, which were fully characterized by field-emission scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffractometry, and vibrating sample magnetometry. The Fe 3 O 4 -SiO 2 nanoparticles were used as the separation media in dispersive solid-phase extraction with primary secondary amine and ZrO 2 as the cleanup adsorbents to eliminate matrix interferences. The amounts of nanoparticles and adsorbents were optimized for the simultaneous determination of 44 pesticides and six metabolites in earthworms by liquid chromatography with tandem mass spectrometry. The method performance was systematically validated with satisfactory results. The limits of quantification were 20 μg/kg for all analytes studied, while the recoveries of the target analytes ranged from 65.1 to 127% with relative standard deviation values lower than 15.0%. The developed method was subsequently utilized to explore the bioaccumulation of bitertanol in earthworms exposed to contaminated soil, verifying its feasibility for real sample analysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-phase extraction of iridium from soil and water samples by using activated carbon cloth prior to its spectrophotometric determination.

PubMed

Ozkantar, Nebiye; Yilmaz, Erkan; Soylak, Mustafa; Tuzen, Mustafa

2015-08-01

A solid-phase extraction method for separation and preconcentration of Ir(IV) ion by using activated carbon cloth (ACC) has been presented. Ir(IV) as their 1-(2-pyridylazo) 2-naphtol (PAN) chelate was adsorbed on ACC at pH 2.0 and was eluted from ACC with acidic dimethylformamide (DMF). The Ir(IV) concentration was determined at 536 nm as Ir(IV)-PAN complex by using UV-vis spectrophotometer. The analytical parameters including pH, sample and eluent flow rates, amount of PAN, eluent type, concentration, and sample volume were optimized. The effects of foreign ions on the recoveries of iridium were also investigated. The preconcentration factor was calculated as 60. The limit of detection (LOD) and the limit of quantification (LOQ) of the method were found as 0.039 and 0.129 μg L(-1), respectively. The method was applied to soil and water samples for iridium determination.

Following The Money: Characterizing the Dynamics of Microbial Ecosystems and Labile Organic Matter in Grassland Soils

NASA Astrophysics Data System (ADS)

Herbert, B. E.; McNeal, K. S.

2006-12-01

The dynamics of soil microbial ecosystems and labile fractions of soil organic matter in grasslands have important implications for the response of these critical ecosystems to perturbations. Organic, inorganic and genetic biomarkers in the solid (e.g. lipids, microbial DNA), liquid (e.g. porewater ions) or gaseous phases (e.g. carbon dioxide) have been used to characterize carbon cycling and soil microbial ecology. These proxies are generally limited in the amount of temporal information that they can provide (i.e., solid-phase proxies) or the amount of specific information they can provide about carbon sources or microbial community processes (e.g. inorganic gases). It is the aim of this research to validate the use of soil volatile organic carbon emissions (VOCs) as useful indicators of subsurface microbial community shifts and processes as a function of ecosystem perturbations. We present results of method validation using laboratory microcosm, where VOC metabolites as characterized by gas chromatography and mass spectrometry (GC-MS), were related to other proxies including carbon dioxide (CO2) via infra-red technology, and microbial community shifts as measured by Biolog© and fatty acid methyl ester (FAME) techniques. Experiments with soil collected from grasslands along the coastal margin region in southern Texas were preformed where environmental factors such as soil water content, soil type, and charcoal content are manipulated. Results indicate that over fifty identifiable VOC metabolites are produced from the soils, where many (~15) can be direct indicators of microbial ecology. Principle component analysis (PCA) evidences these trends through similar cluster patterns for the VOC results, the Biolog© results, and FAME. Regression analysis further shows that VOCs are significant (p < 0.05) indicators of microbial stress. Our results are encouraging that characterizing VOCs production in grassland soils are easy to measure, relatively inexpensive method, and useful proxies of subsurface microbial ecosystems and the dynamics of labile carbon in these systems.

Methylmercury production in soil in the water-level-fluctuating zone of the Three Gorges Reservoir, China: The key role of low-molecular-weight organic acids.

PubMed

Yin, Deliang; Wang, Yongmin; Jiang, Tao; Qin, Caiqing; Xiang, Yuping; Chen, Qiuyu; Xue, Jinping; Wang, Dingyong

2018-04-01

As important parts of dissolved organic matter, low-molecular-weight organic acids (LMWOAs) typically play important roles in desorbing Hg(II) from the soil solid-phase, which may directly or indirectly impact methylmercury (MeHg) production. However, the mechanism of these processes remains unclear. To better understand the effects of LMWOAs on Hg methylation in the soil, a field study was conducted to investigate the distribution of LMWOAs and their relationship with soil MeHg in a seasonally inundated area in the Three Gorges Reservoir (TGR), China. Meanwhile, laboratory simulation experiments were performed to determine the potential mechanism of LMWOAs in Hg methylation. The field investigation detected considerable amounts of LMWOAs in soil, among which tartaric acid and oxalic acid were dominant components. Among which, tartaric acid and oxalic acid were dominant components. Also, a seasonally and spatially heterogeneous distribution of LMWOAs in soil was observed. Notably, a significant positive relationship was found between MeHg concentrations and LMWOA pools in soil (r = 0.969, p < .01), implying that LMWOAs could promote soil MeHg production. The simulation experiments confirmed that the MeHg levels in soil were largely elevated with the addition of LMWOAs, which occurred mainly in oxygen-deficient environment and was mediated by biotic factors. The soluble Hg-LMWOA complexes, which were formed by the enhanced desorption of Hg(II) from solid-phase, were mostly responsible for the elevated MeHg production in soil. Moreover, those LMWOAs with more carboxylic groups were believed to enhance the net production of MeHg. The generated MeHg in sediment could diffuse into the overlying water, which thus poses a potential threat to the aquatic food web. Therefore, the enhanced Hg methylation caused by LMWOAs should be given more attention, especially in a seasonally inundated ecosystem, where the MeHg exposure is usually related to fishery activities. Copyright © 2017 Elsevier Ltd. All rights reserved.

Do Vertical Gradients in Soil Environmental Conditions Regulate Exudation Rates from Peatland Vegetation?

NASA Astrophysics Data System (ADS)

Proctor, C.; He, Y.

2017-12-01

Deposition of carbon belowground via the root exudation pathway is the net of root-borne efflux and influx processes. For select exudates, root have a remarkable ability to actively recapture lost compounds, suggesting that influx mechanisms regulate exudation. However, roots are not the sole sink for root effluxed carbon. Roots compete with solute sorption and microbial uptake, whom are regulated by a unique set of soil environmental conditions. Peatland soil features stark vertical gradients in their physical, chemical, biological, and hydrological properties, which has downstream implications for the relative competitive ability of each actor in root-soil-microbial interactions. This study developed a single root exudate model using the Barber-Cushman approach to examine the radial accumulation of exudates in simulated peatland soil with vertical gradients. The model simulated efflux, influx, solute diffusion, solute mineralization and solid phase sorption mechanisms as depth dependent on bulk density, porosity, tortuosity, buffer power, temperature, and microbial biomass. Deeper peat soil reduced the porosity that permits solute transport, increased tortuosity which lowered the effective diffusion rate, increased solute-solid sorption, and reduced microbial mineralization of effluxed compounds. Slower mineralization rates were partially juxtaposed by increases in sorption, albeit the net removal of effluxed compounds was lower, leading to a larger amount of exudates to remain in the rhizosphere around deeper roots. Increase in the solid phase, and its subsequent constriction of solute migration, lead to a higher accumulation of effluxed compounds on the rhizoplane, up to 1.23x higher than shallow soil. Subsequently, influx mechanisms captured a larger fraction of effluxed compounds (69.06% at -10cm versus 84.8% at -80 cm), reducing net exudation rates from 0.641 to 0.315 nmol cm-1 hr-1 between -10 and -80cm depths. These results suggest that localized environmental conditions around roots can be a considerable influence on root influx and competition for root exudates. The insights provided by this model help provide a better understanding of exudate regulation in peatlands and the quantity and quality of carbon deposited to the methanogen community.

Assessment of nonpoint source chemical loading potential to watersheds containing uranium waste dumps and human health hazards associated with uranium exploration and mining, Red, White, and Fry Canyons, southeastern Utah, 2007

USGS Publications Warehouse

Beisner, Kimberly R.; Marston, Thomas M.; Naftz, David L.; Snyder, Terry; Freeman, Michael L.

2010-01-01

During May, June, and July 2007, 58 solid-phase samples were collected from abandoned uranium mine waste dumps, background sites, and adjacent streambeds in Red, White, and Fry Canyons in southeastern Utah. The objectives of this sampling program were to (1) assess the nonpoint-source chemical loading potential to ephemeral and perennial drainage basins from uranium waste dumps and (2) assess potential effects on human health due to recreational activities on and around uranium waste dumps on Bureau of Land Management property. Uranium waste-dump samples were collected using solid-phase sampling protocols. After collection, solid-phase samples were homogenized and extracted in the laboratory using a leaching procedure. Filtered (0.45 micron) water samples were obtained from the field leaching procedure and were analyzed for major and trace elements at the Inductively Coupled Plasma-Mass Spectrometry Metals Analysis Laboratory at the University of Utah. A subset of the solid-phase samples also were digested with strong acids and analyzed for major ions and trace elements at the U.S. Geological Survey Geologic Division Laboratory in Denver, Colorado. For the initial ranking of chemical loading potential for uranium waste dumps, results of leachate analyses were compared with existing aquatic-life and drinking-water-quality standards. To assess potential effects on human health, solid-phase digestion values for uranium were compared to soil screening levels (SSL) computed using the computer model RESRAD 6.5 for a probable concentration of radium. One or more chemical constituents exceeded aquatic life and drinking-water-quality standards in approximately 64 percent (29/45) of the leachate samples extracted from uranium waste dumps. Most of the uranium waste dump sites with elevated trace-element concentrations in leachates were located in Red Canyon. Approximately 69 percent (31/45) of the strong acid digestible soil concentration values were greater than a calculated SSL. Uranium waste dump sites with elevated leachate and total digestible concentrations may need to be further investigated to determine the most appropriate remediation method.

Reductive solubilization of arsenic in a mining-impacted river floodplain: Influence of soil properties and temperature.

PubMed

Simmler, Michael; Bommer, Jérôme; Frischknecht, Sarah; Christl, Iso; Kotsev, Tsvetan; Kretzschmar, Ruben

2017-12-01

Mining activities have contaminated many riverine floodplains with arsenic (As). When floodplain soils become anoxic under water-saturated conditions, As can be released from the solid phase. Several microbially-driven As solubilization processes and numerous influential factors were recognized in the past. However, the interplay and relative importance of soil properties and the influence of environmental factors such as temperature remain poorly understood, especially considering the (co)variation of soil properties in a floodplain. We conducted anoxic microcosm experiments at 10, 17.5, and 25 °C using 65 representative soils from the mining-impacted Ogosta River floodplain in Bulgaria. To investigate the processes of As solubilization and its quantitative variation we followed the As and Fe redox dynamics in the solid and the dissolved phase and monitored a range of other solution parameters including pH, Eh, dissolved organic C, and dissolved Mn. We related soil properties to dissolved As observed after 20 days of microcosm incubation to identify key soil properties for As solubilization. Our results evidenced reductive dissolution of As-bearing Fe(III)-oxyhydroxides as the main cause for high solubilization. The availability of nutrients, most likely organic C as the source of energy for microorganisms, was found to limit this process. Following the vertical nutrient gradient common in vegetated soil, we observed several hundred μM dissolved As after 1-2 weeks for some topsoils (0-20 cm), while for subsoils (20-40 cm) with comparable total As levels only minor solubilization was observed. While high Mn contents were found to inhibit As solubilization, the opposite applied for higher temperature (Q 10 2.3-6.1 for range 10-25 °C). Our results suggest that flooding of nutrient-rich surface layers might be more problematic than water-saturation of nutrient-poor subsoil layers, especially in summer floodings when soil temperature is higher than in winter or spring. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mobility of Heavy Metals (Pb, Cd, Zn) in the Pampeano and Puelche Aquifers, Argentina: Partition and Retardation Coefficients.

PubMed

Jakomin, L M; Marbán, L; Grondona, S; Glok Galli, M; Martínez, D E

2015-09-01

The prediction about metals behaviour in soil requires knowledge on their solid-liquid partitioning. Usually it is expressed with an empirical distribution coefficient or Kd, which gives the ratio of the metal concentration in the solid phase to that in the solution. Kd values have been determined for Zn, Pb and Cd from samples representing the two most exploited aquifers in Argentina, Pampeano and Puelche, at three different locations in the province of Buenos Aires. The Pampeano aquifer presented higher Kd values than the Puelche aquifer. Comparing Kd values, different relationships could be observed: (a) Pampeano aquifer: Pb > Zn > Cd, and (b) Puelche aquifer: Pb > Cd > Zn. Kd for Cd seems to be linked to cationic exchange capacity, but solid phases precipitation can be more determining for Pb and Zn.

ASSESSMENT OF A SEQUENTIAL EXTRACTION PROCEDURE FOR PERTURBED LEAD-CONTAMINATED SAMPLES WITH AND WITHOUT PHOSPHOROUS AMENDMENTS

EPA Science Inventory

Sequential extraction procedures are used to determine the solid-phase association in which elements of interest exist in soil and sediment matrices. Foundational work by Tessier et al. (1) has found widespread acceptance and has worked tolerably as an operational definition for...

TRANSFORMATION AND MOBILIZATION OF ARSENIC ADSORBED ON GRANULAR FERRIC HYDROXIDE UNDER BIO-REDUCTIVE CONDITIONS

EPA Science Inventory

Biotic and abiotic reduction of arsenic (V) and iron (III) influences the partioning of arsenic (As) between the solid and aqueous phases in soils, sediments and wastes. In this study, laboratory experiments on arsenic adsorbed on granular ferric hydroxide (GFH) was performed to ...

SW-846 Test Method 3200: Mercury Species Fractionation and Quantification by Microwave Assisted Extraction, Selective Solvent Extraction and/or Solid Phase Extraction

EPA Pesticide Factsheets

a sequential extraction and separation procedure that maybe used in conjunction with a determinative method to differentiate mercury species that arepresent in soils and sediments. provides information on both total mercury andvarious mercury species.

EMPIRICAL MODELS OF PB AND CD PARTITIONING USING DATA FROM 13 SOILS, SEDIMENTS AND AQUIFER MATERIALS

EPA Science Inventory

Lead (Pb) and cadmium (Cd) are two of the most common toxicants found in contaminated environments. Because solubilization of these metallic elements from the solid phase can influence their fate, transport and bioavailability, the partitioning coefficient (Kd) for these metals ...

A novel technique to determine cobalt exchangeability in soils using isotope dilution.

PubMed

Wendling, Laura A; Kirby, Jason K; McLaughlin, Michael J

2008-01-01

The environmental risk posed by Co contamination is largely a function of its oxidation state. Our objective was to assess the potential biological availability of Co and the reactions and fate of soluble Co(II) after addition to soils with varying physical and chemical characteristics. A potential risk in quantifying exchangeable Co in soils using isotope dilution techniques is the possible presence of two species of Co in soil solution and adsorbed on soil solid phases [Co(II) and Co(III)], coupled with the possibility that when an isotope of Co is added it may undergo a change in oxidation state during the measurement phase. In this study, we have utilized an isotope dilution technique with cation exchange and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry to determine the isotopically exchangeable Co fraction in several soils with varying characteristics such as differing Al, Fe, and Mn oxide content; pH; and organic carbon content. The application of the cation exchange procedure adjusts measurements of isotopically exchangeable Co to correct for the presence of non-exchangeable 57Co not in equilibrium with the solution phase. Results indicated that oxidation of added 57Co(II) to 57Co(III) or precipitation of 57Co(II) may occur on the surfaces of some soils, particularly those with a high pH or substantial quantities of Mn oxide minerals. No detectable Co(III)(aq) was found in the aqueous extracts of the soils examined.

Optimization of extractants, purifying packings, and eluents for analytical extraction of organochlorine pesticides in Hydragric Acrisols.

PubMed

Zhao, Zhenhua; Xia, Liling; Wang, Fang; Jiang, Xin; Gao, Yanzheng

2012-08-01

In this study, we screened for an economic, rapid, and efficient hypotoxic pretreatment method for organochlorine pesticides in soil samples for gas chromatography (GC) analysis. The analytical extraction efficiencies of 11 different extractants, nine types of solid-phase purification (SPP) cartridge packings, and three types of eluents for 13 organochlorine pesticides (OCPs) in spiked and natural Chinese red soil (Hydragric Acrisols) were evaluated using an ultrasonic extraction and solid-phase purification method. High percent recoveries (85-106%) were obtained for the 13 organochlorine pesticides in soil when petroleum ether/acetone/water (10:5:2, v/v) was used an extractant. They were purified using celite SPP cartridge packing and eluted with 9 mL of dichloromethane/petroleum ether (1:9, v/v). The OCPs purification pretreatment of Hydragric Acrisols, using the above method, meets the GC analysis requirements. Compared with other traditional pretreatment methods for OCPs in soil samples, this method has several advantages, such as a short extraction time, reducing the amount of solvent, having no emulsion phenomenon, and hypotoxicity to the laboratory technicians. The concentrations of 1,1,1,-trichloro-2(p-chlorophenyl)-2-(o-chlorophenyl) ethane (DDTs; 3.42-8.08 ng g(-1)) in field soils were higher than the hexachlorocyclohexane concentration (2.94-6.12 ng g(-1)). The 1,1-dichloro-2,2-bis(p-chlorophenyl) ethylene (p,p'-DDE) + 1,1-dichloro-2,2-bis(p-chlorophenyl)-ethane (p,p'-DDD)/p,p'-DDT ratio in this field soil was approximately 2.7, suggesting that no new DDT pollution source was introduced into the sampling site.

Field Analysis of Polychlorinated Biphenyls (PCBs) in Soil Using Solid-Phase Microextraction (SPME) and a Portable Gas Chromatography-Mass Spectrometry System.

PubMed

Zhang, Mengliang; Kruse, Natalie A; Bowman, Jennifer R; Jackson, Glen P

2016-05-01

An expedited field analysis method was developed for the determination of polychlorinated biphenyls (PCBs) in soil matrices using a portable gas chromatography-mass spectrometry (GC-MS) instrument. Soil samples of approximately 0.5 g were measured with a portable scale and PCBs were extracted by headspace solid-phase microextraction (SPME) with a 100 µm polydimethylsiloxane (PDMS) fiber. Two milliliters of 0.2 M potassium permanganate and 0.5 mL of 6 M sulfuric acid solution were added to the soil matrices to facilitate the extraction of PCBs. The extraction was performed for 30 min at 100 ℃ in a portable heating block that was powered by a portable generator. The portable GC-MS instrument took less than 6 min per analysis and ran off an internal battery and helium cylinder. Six commercial PCB mixtures, Aroclor 1016, 1221, 1232, 1242, 1248, 1254, and 1260, could be classified based on the GC chromatograms and mass spectra. The detection limit of this method for Aroclor 1260 in soil matrices is approximately 10 ppm, which is sufficient for guiding remediation efforts in contaminated sites. This method was applicable to the on-site analysis of PCBs with a total analysis time of 37 min per sample. However, the total analysis time could be improved to less than 7 min per sample by conducting the rate-limiting extraction step for different samples in parallel. © The Author(s) 2016.

Peroxidase-catalyzed stabilization of 2,4-dichlorophenol in alkali-extracted soils.

PubMed

Palomo, Mónica; Bhandari, Alok

2011-01-01

Horseradish peroxidase- (HRP) mediated stabilization of phenolic contaminants is a topic of interest due to its potential for remediation of contaminated soils. This study evaluated the sorption of 2,4-dichlorophenol (DCP) and its HRP-mediated stabilization in two alkali-extracted soils. Alkali extraction reduced the soil organic matter (SOM) contents of the geomaterials and enriched the residual SOM with humin C. Sorption of DCP on these sorbents was complete within 1 d. However, most of the sorbed DCP was removed from the geomaterials by water and methanol, suggesting weak solute-sorbent interactions. The addition of HRP resulted in the generation of DCP polymerization products (DPP), which partitioned between the aqueous and solid phases. The DPP phase distribution was rapid and complete within 24 h. Between 70 and 90% of the added DCP was converted to DPP and up to 43% of the initial aqueous phase contaminant was transformed into a residue that was resistant to extraction with methanol. Bound residues of DPP increased with initial aqueous phase solute concentration and remained fairly constant after 7 d of contact. Contaminant stabilization was noted to be high in the humin-mineral geomaterial. Results illustrate that HRP may be effective in stabilizing phenolic contaminants in subsoils that are likely to contain SOM enriched in humin C.

Characterization of ozone decomposition in a soil slurry: kinetics and mechanism.

PubMed

Lim, Hyung-Nam; Choi, Hechul; Hwang, Tae-Moon; Kang, Joon-Wun

2002-01-01

A series of soil slurry experiments were performed in a carefully conceived reactor set-up to investigate the characteristics of the catalytic decomposition of ozone on a sand and iron surface. Real time on-line monitoring of ozone in the reaction module was possible using flow injection analysis coupled with a computer-controlled UV detector and data acquisition system. The effects of the soil media and size, ozone dosage, pH and p-CBA as a probe compound were examined at the given experimental conditions. Two apparent phases existed, and ozone instantaneously decomposed within one second in the first phase. These were defined as the instantaneous ozone demand (ID) phase, and the relatively slow decay stage. The interactions of ozone with the soil organic matter (SOM) and metal oxides were attributed mostly to the instantaneous decomposition of ozone. From the probe (p-CBA) experiments, 60-68% of total p-CBA removal occurred during the ID phase. The generation of hydroxyl radicals (OH.) was demonstrated and was closely related with metal oxides as well as SOM. Metal oxides in soil surface were considered to have relatively faster reaction rate with ozone and provide more favorable reactive sites to generate higher amount of OH. than SOM. Even at one-tenth concentration of the sands, a goethite-induced catalytic reaction outfitted the removal rate ofp-CBA among all the soils tested. More than 40% of total p-CBA removal occurred on the soil surface. It was inferred that the radical reaction with the probe compound seemed to take place not only on the soil surface but also in the solid-liquid interface. Ozone decomposition and the reaction between OH. and p-CBA appeared to be independent of any change in pH.

Assessment of solid phase microfiber extraction fibers for the monitoring of volatile organoarsinicals emitted from a plant-soil system.

PubMed

Ruppert, L; Lin, Z-Q; Dixon, R P; Johnson, K A

2013-11-15

Phytoremediation, the use of plants and microbes to clean up inorganic and organic pollutants, has shown great promise as an inexpensive and feasible form of remediation. More recently, studies have shown that some plants have an amazing capacity to volatilize contaminants and can be an effective remediation strategy if the chemicals released are non-toxic. Arsenic contamination and remediation has drawn great attention in the scientific community. However, its toxicity also varies depending on its form. We evaluated, optimized, and then utilized a solid phase microfiber extraction (SPME) head space sampling technique to characterize the organoarsinical emissions from rabbitfoot grass (Polypogon monspeliensis) in arsenic treated soils to determine if the potentially more toxic organic forms of arsenic (AsH3, AsH2CH3, AsH(CH3)2, and As(CH3)3) were being emitted from the plant-soil system. The SPME fiber that proved best fitted for this application was the DVB/CAR/PDMS fiber with a 45 min sampling period. We did detect and confirm the emissions of dimethylchloroarsine (AsCl(CH3)2) and pentamethylarsine (As(CH3)5). However, it was determined that the more toxic organic forms of arsenic were not released during phytovolatilization. Copyright © 2012 Elsevier B.V. All rights reserved.

Application of magnetic nanoparticles coated with sodium dodecyl sulfate and modified with 2-(5-bromo-2-pyridylazo)-5-diethyl aminophenol as a novel adsorbent for dispersive-magnetic solid-phase extraction and determination of palladium in soil samples.

PubMed

Wang, Meng; Wu, Lan; Hu, Qiufen; Yang, Yaling

2018-03-01

A rapid, sensitive, precise, and accurate dispersive-magnetic solid-phase extraction technique combined with flame atomic absorption spectrometry was established for pre-concentration and separation of Pd (II) in soil samples. In the developed system, 5-amine-1,10-phenanthroline was used as synergistic complexant; sodium dodecyl sulfate and 2-(5-bromo-2-pyridylazo)-5-diethyl aminophenol ligand coated on magnetic nanoparticles were synthesized by a chemical precipitation method, and then employed as the efficient magnetic adsorbent with good magnetic properties and dispersibility. Various operational parameters affecting the extraction efficiency has been studied and optimized in details. Under the optimum experimental conditions, the detection limit of the mentioned method for palladium ions was 0.12 μg/L, while the relative standard deviation was 1.8%. Finally, the developed method was applied for the analysis of palladium ions in three kinds of soil samples and quantitative recoveries were achieved over the range of 96.7-104.0%. It can be a powerful alternative applied to the determination of traces of Pd ions from various real samples in further researches.

Study on each phase characteristics of the whole coal life cycle and their ecological risk assessment-a case of coal in China.

PubMed

Dai, Wenting; Dong, Jihong; Yan, Wanglin; Xu, Jiren

2017-01-01

The paper divided the whole coal life cycle, explained each phase characteristics, and took coal mine in China as a study case to assess the ecological risk in coal utilization phase. The main conclusions are as follows: (1) the whole coal life cycle is divided into coal mining, processing, transportation, utilization, and waste disposal. (2) The key points of production organization and characteristics in the five phases have great differences. The coal mining phase is characterized by the damage of the key ecological factors (water, soil, atmosphere, vegetation, etc.) damaged while the coal processing phase by discharging waste. The characteristics in coal transportation phase mainly performance as escaping and migration of atmospheric pollutants. In coal utilization phase, the main characteristics are aggravation of greenhouse effect. The main characteristics of waste disposal phase are accumulation of negative ecological effects on the land. (3) The ecological risk of soil heavy metals is serious in coal utilization phase. The potential ecological hazard coefficients of Pb and As in coal, residue and ash are all lower than 40, presenting low environmental impact on soil; the potential ecological risk coefficients of Cd are higher than 60, nearly half of their potential ecological risk coefficients are higher than 160, which presents high environmental pollution impact on soil; Hg's potential ecological risk coefficients are higher than 320, presenting the highest environmental pollution impact on soil; the comprehensive pollution indexes in coal, residue, and ash are relatively high, which means the pollution hazard potential to soil environment is high. (4) The ecological risk of the atmospheric solid suspended matter is relatively strong in coal utilization phase. The ecological risk of Cd and As in primary flue gas is both lower than net flue gas. The geoaccumulation indexes of Cd and Hg in primary flue gas and net flue gas are both higher than 5, presenting the very strong ecological risk; 50 % of the geoaccumulation index values of As are between 3 and 4, which has also presenting a strong ecological risk while Pb does not present the ecological risk characterization.

Quantitative study of the capture of silver nanoparticles by several kinds of soils.

PubMed

González-Fuenzalida, R A; Sanjuan-Navarro, L; Moliner-Martínez, Y; Campíns-Falcó, P

2018-07-15

The capacity of different soils to capture silver nanoparticles (AgNPs) by measuring changes of an AgNP intrinsic property such as the plasmon for the first time, was studied. In-tube solid-phase microextraction (IT-SPME) coupled on-line to capillary liquid chromatography (CapLC) with diode array detection (DAD) was employed for measuring the interactions between soil and in-contact AgNP dispersions. Its achieved LOD 9 pM assures quantitative retention measurements and selectivity for soil lixiviation was suitable. Electronic microscopy was employed for corroborating the entrapped Ag into the soils. Capture % of AgNPs was calculated in compost (>99%), mountain (>99%), orchard (15±1%) and urban (48±1%) soils. Also, the relation between some soil characteristics: solid organic matter (SOM), composition, pH, redox potential (Eh), electrical conductivity (EC) and size, and the retention of these metallic nanoparticles was studied. The results have also been estimated after sieving and the capture % of AgNPs was similar in the resulting fractions. AgNP adsorption on a given soil is mainly affected by its organic matter content for studied soils with higher SOM amounts (23-62%). However, for the soils with lower SOM amounts (4.6-8.3%) the role of HAs could prevent AgNP deposition onto soils. The proposed methodology can be utilized for quickly assessing the potential of a given soil considering its properties for capturing these nanoparticles, which can come at handy for their administration, characterization or remediation. Copyright © 2018 Elsevier B.V. All rights reserved.

Determination of chlorinated acid herbicides in vegetation and soil by liquid chromatography/electrospray-tandem mass spectrometry.

PubMed

Schaner, Angela; Konecny, Jaclyn; Luckey, Laura; Hickes, Heidi

2007-01-01

The method presented uses reversed-phase liquid chromatography with negative electrospray ionization and tandem mass spectrometry to analyze 9 chlorinated acid herbicides in soil and vegetation matrixes: clopyralid, dicamba, MCPP, MCPA, 2,4-DP, 2,4-D, triclopyr, 2,4-DB, and picloram. A 20 g portion is extracted with a basic solution and an aliquot acidified and micropartitioned with 3 mL chloroform. Vegetation samples are subjected to an additional cleanup with a mixed-mode anion exchange solid-phase extraction cartridge. Two precursor product ion transitions per analyte are measured and evaluated to provide the maximum degree of confidence in results. Average recoveries for 3 different soil types tested ranged from 72 to 107% for all compounds with the exception of 2,4-DB at 56-99%. Average recoveries for the 3 different vegetation types studied were lower and ranged from 53 to 80% for all compounds.

Interactions between earthworms and arsenic in the soil environment: a review.

PubMed

Langdon, Caroline J; Piearce, Trevor G; Meharg, Andrew A; Semple, Kirk T

2003-01-01

Chemical pollution of the environment has become a major source of concern. In particular, many studies have investigated the impact of pollution on biota in the environment. Studies on metalliferous contaminated mine spoil wastes have shown that some soil organisms have the capability to become resistant to metal/metalloid toxicity. Earthworms are known to inhabit arsenic-rich metalliferous soils and, due to their intimate contact with the soil, in both the solid and aqueous phases, are likely to accumulate contaminants present in mine spoil. Earthworms that inhabit metalliferous contaminated soils must have developed mechanisms of resistance to the toxins found in these soils. The mechanisms of resistance are not fully understood; they may involve physiological adaptation (acclimation) or be genetic. This review discusses the relationships between earthworms and arsenic-rich mine spoil wastes, looking critically at resistance and possible mechanisms of resistance, in relation to soil edaphic factors and possible trophic transfer routes.

Alternative sorbents for the dispersive solid-phase extraction step in quick, easy, cheap, effective, rugged and safe method for extraction of pesticides from rice paddy soils with determination by liquid chromatography tandem mass spectrometry.

PubMed

Arias, Jean Lucas de Oliveira; Rombaldi, Caroline; Caldas, Sergiane Souza; Primel, Ednei Gilberto

2014-09-19

The clean-up step is essential to reduce interferences, improve quantification and help to maintain the integrity of the chromatographic system when working with complex matrices. In this study, alternative materials were evaluated as sorbents in the dispersive solid-phase extraction (D-SPE) for the determination and extraction of seventeen pesticides from rice paddy soil samples by the quick, easy, cheap, effective, rugged and safe (QuEChERS) method coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Chitin, chitosan, diatomaceous earth and PSA were compared in terms of extraction efficiency and matrix effect. The best results were achieved when chitosan was used. Quantification limits ranged from 0.1 to 100μgkg(-1). Calibration curves showed correlation coefficient values higher than 0.98. Results of accuracy and precision in the spiked soil samples between 60% and 120%, with a relative standard deviation lower than 20%, were reached for 15 out of 17 pesticides. The matrix effect was evaluated and only one compound was influenced by the matrix components, showing medium effect. Results showed that alternative materials are more effective and less expensive than traditional sorbents which have been usually employed, i.e., they may be used in the D-SPE step during the extraction of pesticides from rice paddy soils. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of atrazine and its major degradation products in soil pore water by solid-phase extraction, chemical derivatization, and gas chromatography/mass spectrometry

USGS Publications Warehouse

Carter, D.S.

1996-01-01

This report describes a method for the determination of atrazine, desethylatrazine, deisopropylatrazine, didealkylatrazine, and hydroxyatrazine from soil pore waters by use of solid-phase extractionfollowed by chemical derivatization and gas chromatography/mass spectrometry. The analytes are isolated from the pore-water matrix byextraction onto a graphitized carbon-black cartridge. The cartridge is dried under vacuum, and adsorbed analytes are removed by elution with ethyl acetate followed by dichloromethane/methanol (7:3, volume/volume). Water is removed from the ethyl acetate fraction on an anhydrous sodium sulfate column. The combined fractions are solvent exchanged into acetonitrile, evaporated by use of a nitrogen stream, and derivatized by use of N- methyl-N-(tert-butyldimethylsilyl)- trifluoroacetamide. The derivatized extracts are analyzed by capillary-column gaschromatography/electron-impact mass spectrometry in the scan mode. Estimated method detection limits range from 0.03 to 0.07 micrograms per liter. The mean recoveries of all analytes and surrogates determined at 0.74 to 0.82 micrograms per liter in reagent water in soil pore water were 94 percent and 98 percent, respectively. The mean recoveries of all analytes and surrogates determined at 7.4 to 8.2 micrograms per liter in reagent water and in soil pore water were 96 percent and 97 percent,respectively. Recoveries were 90 percent or higher, regardless of analyte concentration or matrix composition, for all compounds excepthydroxyatrazine, whose recoveries were slightly lower (77 percent) at the low concentration.

Condition of copper and organic matter in the soil contaminated with metal remediation of humic substances.

NASA Astrophysics Data System (ADS)

Kolchanova, Kseniia; Barsova, Natalia; Motuzova, Galina; Stepanov, Andrey; Karpukhin, Mikhail

2017-04-01

The aim of this study was to investigate the forms of copper and transformation of organic matter in the soil under the influence of humic substances (potassium humate, which was obtained from coal). The object of research was the top layer of soil model field experience. Field experiments were carried out in 10-liter plastic containers.The upper layers were constructed artificially as mixture of loam, sand and peat. Below it was a layer of loam, then gravel and under it we installed lysimeters. The experiment was conducted in 3 settings: 1) control, 2) control + Cu, and 3) control + Cu + potassium humate . Copper was deposited into upper layer at soil column construction as dry powder (CuSO4*5H2O), which is 1000mg per kg. Humic substance was introduced on surface as liquid form. The focus was the state of the copper and organic matter of solid and liquid phase. In the solid phase pH, carbon content, the molecular-mass distributions for the organic matter, total (HNO3 conc.+ H2O2; decomposition in a microwave oven) and acid-soluble (1H HNO3) copper content, sequential extraction of copper (1 M MgCl2, acetate buffer pH 4,8 (AAB), 1% EDTA) were determined. For liquid phase characteristics aqueous extract was obtained and identified therein: pH, total activity and copper content and water-soluble organic matter(WOM) amphiphilic properties. The introduction of copper is accompanied by a decrease in pH in soils from 7 to 6,3. The introduction of the humic substance softens this effect. Introducing humic preparation gives an increase in carbon at 0.5%. HS and copper has no significant effect on the molecular-mass distribution of solid organic matter. Only about 4% introduced copper accounted for the exchangeable form (MgCl2) for the variant only copper contaminated. Copper, mainly precipitated as hydroxides, moved in an AAB extract. And compared with the exchangeable forms its quantity increases by 10 times. Still more copper goes into an extract of EDTA, about half of the total. That is, the introduction of humic substances increases the amount of copper associated with organic matter in complexes with high stability constants. The total amount of copper of the results of extraction is 88-96% of the all total content. Water-soluble copper contains only 0.5% of the total. But the introduction of humic substances increases the amount of water-soluble copper is 3 times. This is due to the increase in the content of the WOM by 2.5-3 times, both due to the hydrophobic and hydrophilic factions of WOM. And this leads to a sharp reduction in the activity of copper in the liquid phase. Dual effect of introducing humic substances was obtained on the results of the work. On the one hand the introduction of humic substances contributes the immobilization of copper by increasing the fraction associated with organic matter in the solid phase. On the other hand the introduction of humic substances contributes the mobilization of copper in the liquid phase due to the increase of WOM.

Determination of nonylphenol and nonylphenol ethoxylates in environmental solid samples by ultrasonic-assisted extraction and high performance liquid chromatography-fluorescence detection.

PubMed

Núñez, L; Turiel, E; Tadeo, J L

2007-04-06

A simple and rapid analytical method for the determination of nonylphenol (NP) and nonylphenol ethoxylates (NPEOx) in solid environmental samples has been developed. This method combines an ultrasonic-assisted extraction procedure in small columns and an enrichment step onto C(18) solid-phase extraction cartridges prior to separation using HPLC with fluorescence detection. Method optimization was carried out using soil samples fortified at different concentration levels (from 0.1 to 100 microg/g). Under optimum conditions, 2g of soil was placed in small glass columns and extraction was performed assisted by sonication (SAESC) at 45 degrees C in two consecutive steps of 15 min using a mixture of H(2)O/MeOH (30/70). The obtained extracts were collected, loaded onto 500 mg C(18) cartridges, and analytes were eluted with 3 x 1 ml of methanol and 1 ml of acetonitrile. Finally, sample extracts were evaporated under a nitrogen stream, redissolved in 500 microl H(2)O/AcN (50/50), and passed though a 0.45 microm nylon filter before final determination by HPLC-FL. The developed procedure allowed to achieve quantitative recoveries for NP and NPEOx, and was properly validated. Finally, the method was applied to the determination of these compounds in soils and other environmental solid samples such as sediments, compost and sludge.

Simultaneous determination of a variety of endocrine disrupting compounds in carrot, lettuce and amended soil by means of focused ultrasonic solid-liquid extraction and dispersive solid-phase extraction as simplified clean-up strategy.

PubMed

Mijangos, L; Bizkarguenaga, E; Prieto, A; Fernández, L A; Zuloaga, O

2015-04-10

The present study is focused on the development of an analytical method based on focused ultrasonic solid-liquid extraction (FUSLE) followed by dispersive solid-phase extraction (dSPE) clean-up and liquid chromatography-triple quadrupole tandem mass spectrometry (LC-MS/MS) optimised for the simultaneous analysis of certain endocrine disrupting compounds (EDCs), including alkylphenols (APs), bisphenol A (BPA), triclosan (TCS) and several hormones and sterols in vegetables (lettuce and carrot) and amended soil samples. Different variables affecting the chromatographic separation, the electrospray ionisation and mass spectrometric detection were optimised in order to improve the sensitivity of the separation and detection steps. Under the optimised extraction conditions (sonication of 5min at 33% of power with pulse times on of 0.8s and pulse times off of 0.2s in 10mL of n-hexane:acetone (30:70, v:v) mixture using an ice bath), different dSPE clean-up sorbents, such as Florisil, Envi-Carb, primary-secondary amine bonded silica (PSA) and C18, or combinations of them were evaluated for FUSLE extracts before LC-MS/MS. Apparent recoveries and precision in terms of relative standard deviation (RSDs %) of the method were determined at two different fortification levels (according to the matrix and the analyte) and values in the 70-130% and 2-27% ranges, respectively, were obtained for most of the target analytes and matrices. Matrix-matched calibration approach and the use of labelled standards as surrogates were needed for the properly quantification of most analytes and matrices. Method detection limits (MDLs), estimated with fortified samples, in the ranges of 0.1-100ng/g for carrot, 0.2-152ng/g for lettuce and 0.9-31ng/g for amended soil were obtained. The developed methodology was applied to the analysis of 11 EDCs in both real vegetable bought in a local market and in compost (from a local wastewater treatment plant, WWTP) amended soil samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Influences of solution chemical conditions on mobilization of TNT from contaminated soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dante, D.A.; Tiller, C.L.; Pennell, K.D.

1996-12-31

Residual explosives and their byproducts are common contaminants at several US military installations. One of the major explosive contaminants is 2,4,6-Trinitrotoluene (TNT) (a hydrophobic organic compound). Contamination from TNT has resulted from manufacturing and handling processes which occurred at military installations, especially Army Ammunition Plants (AAP), over many decades until environmental regulations were implemented. TNT causes adverse effects to the environment, including growth inhibition to plants, toxicity to aquatic life, and possible mutagenicity, and also is toxic to humans. As a result of the effects of TNT on the environment and current environmental regulations, substantial research effort has been focusedmore » on determining the fate of TNT in natural systems and the development of remediation processes. Many potential remediation processes, such as those involving plants or microorganisms, are in part limited by the transfer of TNT from solid phases (e.g., sorbed to soil or present as TNT granules) to the aqueous phase. The purpose of this research is to assess the release of TNT from a soil phase to a mobile aqueous phase under varying solution chemical conditions. In particular, influences of pH, aquatic natural organic matter, and surfactants are investigated.« less

Influence of indian mustard (Brassica juncea) on rhizosphere soil solution chemistry in long-term contaminated soils: a rhizobox study.

PubMed

Kim, Kwon-Rae; Owens, Gary; Kwon, Soon-lk

2010-01-01

This study investigated the influence of Indian mustard (Brassica juncea) root exudation on soil solution properties (pH, dissolved organic carbon (DOC), metal solubility) in the rhizosphere using a rhizobox. Measurement was conducted following the cultivation of Indian mustard in the rhizobox filled four different types of heavy metal contaminated soils (two alkaline soils and two acidic soils). The growth of Indian mustard resulted in a significant increase (by 0.6 pH units) in rhizosphere soil solution pH of acidic soils and only a slight increase (< 0.1 pH units) in alkaline soils. Furthermore, the DOC concentration increased by 17-156 mg/L in the rhizosphere regardless of soil type and the extent of contamination, demonstrating the exudation of DOC from root. Ion chromatographic determination showed a marked increase in the total dissolved organic acids (OAs) in rhizosphere. While root exudates were observed in all soils, the amount of DOC and OAs in soil solution varied considerably amongst different soils, resulting in significant changes to soil solution metals in the rhizosphere. For example, the soil solution Cd, Cu, Pb, and Zn concentrations increased in the rhizosphere of alkaline soils compared to bulk soil following plant cultivation. In contrast, the soluble concentrations of Cd, Pb, and Zn in acidic soils decreased in rhizosphere soil when compared to bulk soils. Besides the influence of pH and DOC on metal solubility, the increase of heavy metal concentration having high stability constant such as Cu and Pb resulted in a release of Cd and Zn from solid phase to liquid phase.

Arsenic in the soils of Zimapán, Mexico.

PubMed

Ongley, Lois K; Sherman, Leslie; Armienta, Aurora; Concilio, Amy; Salinas, Carrie Ferguson

2007-02-01

Arsenic concentrations of 73 soil samples collected in the semi-arid Zimapán Valley range from 4 to 14 700 mg As kg(-1). Soil arsenic concentrations decrease with distance from mines and tailings and slag heaps and exceed 400 mg kg(-1) only within 500 m of these arsenic sources. Soil arsenic concentrations correlate positively with Cu, Pb, and Zn concentrations, suggesting a strong association with ore minerals known to exist in the region. Some As was associated with Fe and Mn oxyhydroxides, this association is less for contaminated than for uncontaminated samples. Very little As was found in the mobile water-soluble or exchangeable fractions. The soils are not arsenic contaminated at depths greater than 100 cm below the surface. Although much of the arsenic in the soils is associated with relatively immobile solid phases, this represents a long-term source of arsenic to the environment.

Wettability, soil organic matter and structure-properties of typical chernozems under the forest and under the arable land

NASA Astrophysics Data System (ADS)

Bykova, Galina; Umarova, Aminat; Tyugai, Zemfira; Milanovskiy, Evgeny; Shein, Evgeny

2017-04-01

Intensive tillage affects the properties of soil: decrease in content of soil organic matter and in hydrophobicity of the soil's solid phase, the reduction of amount of water stable aggregates - all this leads to deterioration of the structure of the soil and affects the process of movement of moisture in the soil profile. One of the hypotheses of soil's structure formation ascribes the formation of water stable aggregates with the presence of hydrophobic organic substances on the surface of the soil's solid phase. The aim of this work is to study the effect of tillage on properties of typical chernozems (pachic Voronic Chernozems, Haplic Chernozems) (Russia, Kursk region), located under the forest and under the arable land. The determination of soil-water contact angle was performed by a Drop Shape Analyzer DSA100 (Krüss GmbH, Germany) by the static sessile drop method. For all samples the content of total and organic carbon by dry combustion in oxygen flow and the particle size distribution by the laser diffraction method on the device Analysette 22 comfort, FRITCH, Germany were determined. The estimation of aggregate composition was performed by dry sieving (AS 200, Retsch, Germany), the content of water stable aggregates was estimated by the Savvinov method. There was a positive correlation between the content of organic matter and soil's wettability in studied soils, a growth of contact angle with the increasing the content of organic matter. Under the forest the content of soil organic matter was changed from 6,41% on the surface up to 1,9% at the depth of 100 cm. In the Chernozem under the arable land the organic carbon content in arable horizon is almost two times less. The maximum of hydrophobicity (78.1o) was observed at the depth of 5 cm under the forest. In the profile under the arable land the contact angle value at the same depth was 50o. The results of the structure analysis has shown a decrease in the content of agronomically valuable and water stable aggregates in the profile under arable land. These data indicate the correlation between the wettability of soils with the content of organic matter and their influence on the formation of water stable structure, as well as the negative impact of tillage on the analyzed characteristics.

Metals other than uranium affected microbial community composition in a historical uranium-mining site.

PubMed

Sitte, Jana; Löffler, Sylvia; Burkhardt, Eva-Maria; Goldfarb, Katherine C; Büchel, Georg; Hazen, Terry C; Küsel, Kirsten

2015-12-01

To understand the links between the long-term impact of uranium and other metals on microbial community composition, ground- and surface water-influenced soils varying greatly in uranium and metal concentrations were investigated at the former uranium-mining district in Ronneburg, Germany. A soil-based 16S PhyloChip approach revealed 2358 bacterial and 35 archaeal operational taxonomic units (OTU) within diverse phylogenetic groups with higher OTU numbers than at other uranium-contaminated sites, e.g., at Oak Ridge. Iron- and sulfate-reducing bacteria (FeRB and SRB), which have the potential to attenuate uranium and other metals by the enzymatic and/or abiotic reduction of metal ions, were found at all sites. Although soil concentrations of solid-phase uranium were high, ranging from 5 to 1569 μg·g (dry weight) soil(-1), redundancy analysis (RDA) and forward selection indicated that neither total nor bio-available uranium concentrations contributed significantly to the observed OTU distribution. Instead, microbial community composition appeared to be influenced more by redox potential. Bacterial communities were also influenced by bio-available manganese and total cobalt and cadmium concentrations. Bio-available cadmium impacted FeRB distribution while bio-available manganese and copper as well as solid-phase zinc concentrations in the soil affected SRB composition. Archaeal communities were influenced by the bio-available lead as well as total zinc and cobalt concentrations. These results suggest that (i) microbial richness was not impacted by heavy metals and radionuclides and that (ii) redox potential and secondary metal contaminants had the strongest effect on microbial community composition, as opposed to uranium, the primary source of contamination.

Using DTPA-extractable soil fraction to assess the bioconcentration factor of plants in phytoremediation of urban soils

NASA Astrophysics Data System (ADS)

Rodríguez-Bocanegra, Javier; Roca, Núria; Tume, Pedro; Bech, Jaume

2017-04-01

Urban soils may be highly contaminated with potentially toxic metals, as a result of intensive anthropogenic activities. Developing cities are increasing the number of lands where is practiced the urban agriculture. In this way, it is necessary to assess the part of heavy metals that is transferred to plants in order to a) know the potential health risk that represent soils and b) know the relation soil-plant to assess the ability of these plants to remove heavy metals from soil. Nowadays, to assess the bioconcentration factor (BF) of plants in phytoremediation, the pseudototal o total concentration has been used by many authors. Two different urban soils with similar pH and carbonates content but with different pollution degree were phytoremediated with different plant species. Urban soil from one Barcelona district (Spain), the most contaminated soil, showed an extractability of Cu, Pb and Zn of 9.6, 6.7 and 5.8% of the total fraction respectively. The soil from Talcahuano city (Chile), with contents of heavy metals slightly above the background upper limit, present values of 15.5, 13.5 and 12% of the total fraction of studied heavy metals. Furthermore, a peri-urban analysed soil from Azul (Argentina) also showed an elevated extractability with values of 24, 13.5 and 14% of the Cu, Pb and Zn contents respectively. These soils presented more extractability than other disturbed soils, like for example, soils from mine areas. The urban soils present more developed soil with an interaction between solution and solid phase in polluted systems. The most important soil surface functional groups include the basal plane of phyllosilicates and metal hydroxyls at edge sites of clay minerals, iron oxyhydroxides, manganese oxyhydroxides and organic matter. The interaction between solution and solid phase in polluted urban systems tends to form labile associations and pollutants are more readily mobilized because their bonds with soil particles are weaker. Clay and organic carbon content are generally considered the most important factors when evaluating the heavy metal content of soils. Therefore, it could be essential to find a soil extractant with the capacity of isolate and extract heavy metals from this soil phase. The extraction methods, e.g. DTPA, have been widely and successfully applied in the study of nutrients elements deficiency in agricultural crops. These extraction methods could be some excellent methods of assessment of potential bioaccumulation capacity of phytoremediation plants in polluted cases. BF-DTPA FRACTION index was >1 in all plants that grew in the urban soil from Talcahuano (Chile), and in too many cases, it was >1 in soil from Sants district (Spain). However, these values were slightly <1 using BF-TOTAL FRACTION index. Thus, so many plants would be being considered non hyperaccumulator plants when the reality is that these plants are uptaking hazardous trace elements in significant quantities. The bioavailable fraction should be considered to define bioconcentration factor as the fraction to assess the potential likelihood of heavy metal mobility and availability with all the implications for toxicity problems.

A Geochemical Reaction Model for Titration of Contaminated Soil and Groundwater at the Oak Ridge Reservation

NASA Astrophysics Data System (ADS)

Zhang, F.; Parker, J. C.; Gu, B.; Luo, W.; Brooks, S. C.; Spalding, B. P.; Jardine, P. M.; Watson, D. B.

2007-12-01

This study investigates geochemical reactions during titration of contaminated soil and groundwater at the Oak Ridge Reservation in eastern Tennessee. The soils and groundwater exhibits low pH and high concentrations of aluminum, calcium, magnesium, manganese, various trace metals such as nickel and cobalt, and radionuclides such as uranium and technetium. The mobility of many of the contaminant species diminishes with increasing pH. However, base additions to increase pH are strongly buffered by various precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior and associated geochemical effects is thus critical to evaluate remediation performance of pH manipulation strategies. This study was undertaken to develop a practical but generally applicable geochemical model to predict aqueous and solid-phase speciation during soil and groundwater titration. To model titration in the presence of aquifer solids, an approach proposed by Spalding and Spalding (2001) was utilized, which treats aquifer solids as a polyprotic acid. Previous studies have shown that Fe and Al-oxyhydroxides strongly sorb dissolved Ni, U and Tc species. In this study, since the total Fe concentration is much smaller than that of Al, only ion exchange reactions associated with Al hydroxides are considered. An equilibrium reaction model that includes aqueous complexation, precipitation, ion exchange, and soil buffering reactions was developed and implemented in the code HydroGeoChem 5.0 (HGC5). Comparison of model results with experimental titration curves for contaminated groundwater alone and for soil- water systems indicated close agreement. This study is expected to facilitate field-scale modeling of geochemical processes under conditions with highly variable pH to develop practical methods to control contaminant mobility at geochemically complex sites.

The potential of flow-through microdialysis for probing low-molecular weight organic anions in rhizosphere soil solution.

PubMed

Sulyok, Michael; Miró, Manuel; Stingeder, Gerhard; Koellensperger, Gunda

2005-08-01

In this paper, flow-through microdialysis is presented as a novel analytical tool for automatic sampling of low molecular weight organic anions (LMWOA), such as oxalate and citrate, in solid samples of environmental concern. The microsampling methodology involves the implantation of dedicated capillary-type probes offering unrivalled spatial resolution (ca. 200μm) in definite soil sites. These passive samplers are aimed at monitoring local processes, such as the release of organic acids occurring in the rhizosphere environment, in nearly real-time. The influence of chemical and physical variables (composition and flow rate of the perfusion liquid, ionic strength and pH of the outer medium and presence of metal ions therein) was assessed in vitro using liquid-phase assays. On the other hand, the resistance of the external solid medium to mass transfer, and the actual applicability of in vivo calibration methods were investigated using quartz sand as an inert model soil. Microdialysers furnished with 3cm long semipermeable tubular membranes were perfused with 0.01M NaNO 3 at a flow rate of 2.0μl/min, yielding dialysis recoveries ≥45% for both assayed LMWOAs in simulated background soil electrolyte solutions, and ≥24% in the interstitial liquid of complex solid samples. Full knowledge of the fate of LMWOAs in soils was obtained through the application of stimulus-response approaches that mimic the discrete exudation pulses of roots. Highly time-resolved microdialysates were used to discern readily available species such as free carboxylic anions and LMW metal-organic acid complexes from adsorbed, precipitated or mineralised analyte species in a variety of soil samples containing variable amounts of organic matter, exchangeable cations and different levels of metal pollution.

An Isotopic Exchange Kinetic Model to Assess the Speciation of Metal Available Pool in Soil: The Case of Nickel.

PubMed

Zelano, I O; Sivry, Y; Quantin, C; Gélabert, A; Maury, A; Phalyvong, K; Benedetti, M F

2016-12-06

In this study an innovative approach is proposed to predict the relative contribution of each mineral phase to the total metal availability in soils, which, in other words, could be called the available metal fractionation. Through the use of isotopic exchange kinetics (IEK) performed on typical Ni bearing phases (i.e., two types of serpentines, chlorite, smectite, goethite, and hematite) the isotopic exchange and metal-solid interaction processes are connected, considering both the thermodynamic and kinetic aspects. Results of Ni IEK experiments on mineral phases are fitted with a pseudo-first order kinetic model. For each Ni bearing phase, this allows to (i) determine the number and size of exchangeable pools (E Ni(i) ), (ii) assess their corresponding kinetic constants (k (i) ), and (iii) discuss the mechanism of Ni isotopic exchange at mineral surfaces. It is shown that all the phases investigated, with the only exception of hematite, present at least two distinct reactive pools with significantly different k (i) values. Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange between 100 and 1000 times faster than metal involved in inner-sphere complexes, and that the presence of high and low affinity sites may influence the rate of isotopic exchange up to 1 order of magnitude. Moreover, the method developed represents a tool to predict and estimate Ni mobility and availability in natural soil samples on the basis of soil mineral composition, providing information barely obtained with other techniques.

Coupled discrete element and finite volume solution of two classical soil mechanics problems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Feng; Drumm, Eric; Guiochon, Georges A

One dimensional solutions for the classic critical upward seepage gradient/quick condition and the time rate of consolidation problems are obtained using coupled routines for the finite volume method (FVM) and discrete element method (DEM), and the results compared with the analytical solutions. The two phase flow in a system composed of fluid and solid is simulated with the fluid phase modeled by solving the averaged Navier-Stokes equation using the FVM and the solid phase is modeled using the DEM. A framework is described for the coupling of two open source computer codes: YADE-OpenDEM for the discrete element method and OpenFOAMmore » for the computational fluid dynamics. The particle-fluid interaction is quantified using a semi-empirical relationship proposed by Ergun [12]. The two classical verification problems are used to explore issues encountered when using coupled flow DEM codes, namely, the appropriate time step size for both the fluid and mechanical solution processes, the choice of the viscous damping coefficient, and the number of solid particles per finite fluid volume.« less

PAH sorption mechanism and partitioning behavior in lampblack-impacted soils from former oil-gas plant sites.

PubMed

Hong, Lei; Ghosh, Upal; Mahajan, Tania; Zare, Richard N; Luthy, Richard G

2003-08-15

This study assessed polycyclic aromatic hydrocarbon (PAH) association and aqueous partitioning in lampblack-impacted field soils from five sites in California that formerly housed oil-gas process operations. Lampblack is the solid residue resulting from the decomposition of crude oil at high temperatures in the gas-making operation and is coated or impregnated with oil gasification byproducts, among which PAHs are the compounds of the greatest regulatory concern. A suite of complementary measurements investigated the character of lampblack particles and PAH location and the associated effects on PAH partitioning between lampblack and water. PAH analyses on both whole samples and density-separated components demonstrated that 81-100% of PAHs in the lampblack-impacted soils was associated with lampblack particles. FTIR, 13C NMR, and SEM analyses showed that oil-gas lampblack solids comprise primarily aromatic carbon with soot-like structures. A free-phase aromatic oil may be present in some of the lampblack soils containing high PAH concentrations. Comparable long-term aqueous partitioning measurements were obtained with an air-bridge technique and with a centrifugation/alum flocculation procedure. Large solid/water partition coefficient (Kd) values were observed in samples exhibiting lower PAH and oil levels, whereas smaller Kd values were measured in lampblack samples containing high PAH levels. The former result is in agreement with an oil-soot partitioning model, and the latter is in agreement with a coal tar-water partitioning model. Lampblack containing high PAH levels appears to exhaust the sorption capacity of the soot-carbon, creating a free aromatic oil phase that exhibits partitioning behavior similar to PAHs in coal tar. This study improves mechanistic understanding of PAH sorption on aged lampblack residuals at former oil-gas sites and provides a framework for mechanistic assessment of PAH leaching potential and risk from such site materials.

Assessment of nonpoint source chemical loading potential to watersheds containing uranium waste dumps associated with uranium exploration and mining, Browns Hole, Utah

USGS Publications Warehouse

Marston, Thomas M.; Beisner, Kimberly R.; Naftz, David L.; Snyder, Terry

2012-01-01

During August of 2008, 35 solid-phase samples were collected from abandoned uranium waste dumps, undisturbed geologic background sites, and adjacent streambeds in Browns Hole in southeastern Utah. The objectives of this sampling program were (1) to assess impacts on human health due to exposure to radium, uranium, and thorium during recreational activities on and around uranium waste dumps on Bureau of Land Management lands; (2) to compare concentrations of trace elements associated with mine waste dumps to natural background concentrations; (3) to assess the nonpoint source chemical loading potential to ephemeral and perennial watersheds from uranium waste dumps; and (4) to assess contamination from waste dumps to the local perennial stream water in Muleshoe Creek. Uranium waste dump samples were collected using solid-phase sampling protocols. Solid samples were digested and analyzed for major and trace elements. Analytical values for radium and uranium in digested samples were compared to multiple soil screening levels developed from annual dosage calculations in accordance with the Comprehensive Environmental Response, Compensation, and Liability Act's minimum cleanup guidelines for uranium waste sites. Three occupancy durations for sites were considered: 4.6 days per year, 7.0 days per year, and 14.0 days per year. None of the sites exceeded the radium soil screening level of 96 picocuries per gram, corresponding to a 4.6 days per year exposure. Two sites exceeded the radium soil screening level of 66 picocuries per gram, corresponding to a 7.0 days per year exposure. Seven sites exceeded the radium soil screening level of 33 picocuries per gram, corresponding to a 14.0 days per year exposure. A perennial stream that flows next to the toe of a uranium waste dump was sampled, analyzed for major and trace elements, and compared with existing aquatic-life and drinking-water-quality standards. None of the water-quality standards were exceeded in the stream samples.

Development and validation of a solid phase extraction sample cleanup procedure for the recovery of trace levels of nitro-organic explosives in soil.

PubMed

Thomas, Jennifer L; Donnelly, Christopher C; Lloyd, Erin W; Mothershead, Robert F; Miller, Mark L

2018-03-01

An improved cleanup method has been developed for the recovery of trace levels of 12 nitro-organic explosives in soil, which is important not only for the forensic community, but also has environmental implications. A wide variety of explosives or explosive-related compounds were evaluated, including nitramines, nitrate esters, nitroaromatics, and a nitroalkane. Fortified soil samples were extracted with acetone, processed via solid phase extraction (SPE), and then analyzed by gas chromatography with electron capture detection. The following three SPE sorbents in cartridge format were compared: Empore™ SDB-XC, Oasis ® HLB, and Bond Elut NEXUS cartridges. The NEXUS cartridges provided the best overall recoveries for the 12 explosives in potting soil (average 48%) and the fastest processing times (<30min). It also rejected matrix components from spent motor oil on potting soil. The SPE method was validated by assessing limit of detection (LOD), processed sample stability, and interferences. All 12 compounds were detectable at 0.02μg explosive/gram of soil or lower in the three matrices tested (potting soil, sand, and loam) over three days. Seven explosives were stable up to seven days at 2μg/g and three were stable at 0.2μg/g, both in processed loam, which was the most challenging matrix. In the interference study, five interferences above the determined LOD for soil were detected in matrices collected across the United States and in purchased all-purpose sand, potting soil, and loam. This represented a 3.2% false positive rate for the 13 matrices processed by the screening method for interferences. The reported SPE cleanup method provides a fast and simple extraction process for separating organic explosives from matrix components, facilitating sample throughput and reducing instrument maintenance. In addition, a comparison study of the validated SPE method versus conventional syringe filtration was completed and highlighted the benefits of sample cleanup for removing matrix interferences, while also providing lower supply cost, order of magnitude lower LODs for most explosives, higher percent recoveries for complex matrices, and fewer instrument maintenance issues. Published by Elsevier B.V.

Detection and quantification of ionophore antibiotics in runoff, soil and poultry litter.

PubMed

Sun, Peizhe; Barmaz, Delphine; Cabrera, Miguel L; Pavlostathis, Spyros G; Huang, Ching-Hua

2013-10-18

Ionophore antibiotics (IPAs) are widely used as coccidiostats in poultry and other livestock industries to promote growth and prevent infections. Because most of the ingested IPAs are excreted in poultry litter, which is primarily applied as grassland fertilizer, a significant amount of IPAs can be released into the litter-soil-water environment. A robust analytical method has been developed to quantify IPAs (monensin (MON), salinomycin (SAL) and narasin (NAR)) in complex environmental compartments including surface runoff, soil and poultry litter, with success to minimize matrix interference. The method for water samples involves solid-phase extraction (SPE) followed by liquid-liquid extraction (LLE) post-clean up steps. The method for solid samples involves bi-solvent LLE. IPAs were detected by HPLC-MS, with optimized parameters to achieve the highest sensitivity. Nigericin (NIG), an IPA not used in livestock industry, is successfully applied and validated as a surrogate standard. The method recoveries were at 92-95% and 81-85% in runoff samples from unfertilized and litter-fertilized fields, respectively. For solids, the method recoveries were at 93-99% in soils, and 79-83% in poultry litter samples. SAL was detected at up to 22mg/kg and MON and NAR at up to 4mg/kg in broiler litter from different farms. Up to 183μg/kg of MON was detected in litter-fertilized soils. All three IPAs were detected in the rainfall runoff from litter-fertilized lands at concentrations up to 9μg/L. Copyright © 2013 Elsevier B.V. All rights reserved.

Measurement of Polycyclic Aromatic Hydrocarbons in Airborne Particulate Matter at Low Concentrations

DTIC Science & Technology

2012-03-01

Soil & Water Colorimetric (diphenylcarbazide) 7199 Hexavalent Chromium by Ion Chromatography 218.6 Low level chelation & extraction NATTS...Hexane:Dichloromethane:Methanol Dionex ASE 200 Sample Concentration Evaporation in Ultrapure Nitrogen Stream Zymark Turbovap Solid Phase Extraction Supelco Custom...Glass Silica SPE Cartridge 1% Dichloromethane + 1% Acetone in Hexane GCMS Analysis Conventional Splitless Injection Selective Ion Monitoring

Modelling chemical degradation of concrete during leaching with rain and soil water types

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacques, D., E-mail: djacques@sckcen.b; Wang, L.; Martens, E.

2010-08-15

Percolation of external water through concrete results in the degradation of cement and changes the concrete pore water and solid phase composition. The assessment of long-term degradation of concrete is possible by means of model simulation. This paper describes simulations of chemical degradation of cement for different types of rain and soil water at an ambient earth surface temperature (10 {sup o}C). Rain and soil water types were derived using generic equations and measurement of atmospheric boundary conditions representative for North-Belgium. An up-to-date and consistent thermodynamic model is used to calculate the geochemical changes during chemical degradation of the concrete.more » A general pattern of four degradation stages was simulated with the third stage being the geochemically most complex stage involving reactions with calcium-silicate hydrates, AFm and AFt phases. Whereas the sequence of the dissolution reactions was relatively insensitive to the composition of the percolating water, the duration of the different reactions depends strongly on the percolating water composition. Major identified factors influencing the velocity of cement degradation are the effect of dry deposition and biological activity increasing the partial pressure of CO{sub 2(g)} in the soil air phase (and thus increasing the inorganic carbon content in the percolating water). Soil weathering processes have only a minor impact, at least for the relatively inert sandy material considered in this study.« less

Plutonium partitioning in three-phase systems with water, granite grains, and different colloids.

PubMed

Xie, Jinchuan; Lin, Jianfeng; Zhou, Xiaohua; Li, Mei; Zhou, Guoqing

2014-01-01

Low-solubility contaminants with high affinity for colloid surfaces may form colloid-associated species. The mobile characteristics of this species are, however, ignored by the traditional sorption/distribution experiments in which colloidal species contributed to the immobile fraction of the contaminants retained on the solids as a result of centrifugation or ultrafiltration procedures. The mobility of the contaminants in subsurface environments might be underestimated accordingly. Our results show that colloidal species of (239)Pu in three-phase systems remained the highest percentages in comparison to both the dissolved species and the immobile species retained on the granite grains (solid phase), although the relative fraction of these three species depended on the colloid types. The real solid/liquid distribution coefficients (K s/d) experimentally determined were generally smaller than the traditional K s/d (i.e., the K s+c/d in this study) by ~1,000 mL/g for the three-phase systems with the mineral colloids (granite particle, soil colloid, or kaolinite colloid). For the humic acid system, the traditional K s/d was 140 mL/g, whereas the real K s/d was approximately zero. The deviations from the real solid/liquid K s/d were caused by the artificially increased immobile fraction of Pu. One has to be cautious in using K s/d-based transport models to predict the fate and transport of Pu in the environment.

Soil quality changes in response to their pollution by heavy metals, Georgia.

PubMed

Matchavariani, Lia; Kalandadze, Besik; Lagidze, Lamzira; Gokhelashvili, Nino; Sulkhanishvili, Nino; Paichadze, Nino; Dvalashvili, Giorgi

2015-01-01

The present study deals with the composition, migration and accumulation of heavy metals in irrigated soils, plants and partially natural waters; and also, establishing the possible sources of pollution and their impact on environmental situation. The content of toxic elements in the irrigated soils adjacent to ore mining and processing enterprise were studied. Content of toxic elements in the irrigated soils adjacent to ore mining, showed that more than half of territory was seriously polluted by copper and zinc. Some part of the area were considered catastrophically polluted. Expressed technogenesis taking place influenced irrigation. Heavy metals like copper, zinc and manganese negative by effected the properties of soil, thus composition and soil-forming processes taking place in the soil. It was especially well represented in the deterioration of hydro-physical potential of the soil. Irrigation of agricultural land plots by water, polluted with heavy metals changed the pH. Balanced correlation among solid, liquid and gas phases was disrupted. In highly polluted soil, the cementing processes took place that sharply increased the bulk density of the soil, deteriorated the porosity of soil and reduced water permeability critically.

First X-Ray Diffraction Results from Mars Science Laboratory: Mineralogy of Rocknest Aeolian Bedform at Gale Crater

NASA Technical Reports Server (NTRS)

Bish, D. L.; Blake, D. F.; Vaniman, D. T.; Chipera, S. J.; Sarrazin, P.; Morris, R. V.; Ming, D. W.; Treiman, A. H.; Downs, R. T.; Morrison, S. M.;

Assessment of a geochemical extraction procedure to determine the solid phase fractionation and bioaccessibility of potentially harmful elements in soils: a case study using the NIST 2710 reference soil.

PubMed

Wragg, Joanna; Cave, Mark

2012-04-13

Three mineral acid sequential extraction regimes (HNO(3) only, HNO(3) followed by HCl and aqua regia) were applied to the NIST 2710 contaminated reference soil. The major and trace element chemical analysis data from the extractions were subjected to a chemometric self-modelling mixture resolution procedure which identified that 12 distinct physico-chemical components were extracted. The fractionation of As, Cd, Ni and Pb between these components were determined. Tentative assignments of the mineralogical sources of the components were made. The human ingestion bioaccessible fraction of As, Cd and Pb were determined using the in vitro BARGE UBM bioaccessibility test and were found to be 51.6%, 68.0% and 68.4% respectively. The relationship between the lability of the physico-chemical components and the bioaccessible fraction of the soils was investigated and the bioaccessible fractions were assigned to specific components. The extraction scheme using aqua regia was found to be the most suitable as it was the only one which extracted the iron sulphide phase in the soil. Copyright © 2012 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Favorito, Jessica E.; Luxton, Todd P.; Eick, Matthew J.

Selenium is a trace element found in western US soils, where ingestion of Se-accumulating plants has resulted in livestock fatalities. Therefore, a reliable understanding of Se speciation and bioavailability is critical for effective mitigation. Sequential extraction procedures (SEP) are often employed to examine Se phases and speciation in contaminated soils but may be limited by experimental conditions. We examined the validity of a SEP using X-ray absorption spectroscopy (XAS) for both whole and a sequence of extracted soils. The sequence included removal of soluble, PO4-extractable, carbonate, amorphous Fe-oxide, crystalline Fe-oxide, organic, and residual Se forms. For whole soils, XANES analysesmore » indicated Se(0) and Se(-II) predominated, with lower amounts of Se(IV) present, related to carbonates and Fe-oxides. Oxidized Se species were more elevated and residual/elemental Se was lower than previous SEP results from ICP-AES suggested. For soils from the SEP sequence, XANES results indicated only partial recovery of carbonate, Fe-oxide and organic Se. This suggests Se was incompletely removed during designated extractions, possibly due to lack of mineral solubilization or reagent specificity. Selenium fractions associated with Fe-oxides were reduced in amount or removed after using hydroxylamine HCl for most soils examined. XANES results indicate partial dissolution of solid-phases may occur during extraction processes. This study demonstrates why precautions should be taken to improve the validity of SEPs. Mineralogical and chemical characterizations should be completed prior to SEP implementation to identify extractable phases or mineral components that may influence extraction effectiveness. Sequential extraction procedures can be appropriately tailored for reliable quantification of speciation in contaminated soils.« less

Determination of neonicotinoid insecticides in environmental samples by micellar electrokinetic chromatography using solid-phase treatments.

PubMed

Ettiene, Gretty; Bauza, Roberto; Plata, María R; Contento, Ana M; Ríos, Angel

2012-10-01

A sensitive and reliable method based on MEKC has been developed and validated for trace determination of neonicotinoid insecticides (thiamethoxam, acetamiprid, and imidacloprid) and the metabolite 6-chloronicotinic acid in water and soil matrices. Optimum separation of the neonicotinoid insecticides was obtained on a 58 cm long capillary (75 μm id) using as the running electrolyte 40 mM SDS, 5 mM borate (pH 10.4), and 5% (v/v) methanol at a temperature of 25°C, a voltage of 25 kV and with hydrodynamic injection (10 s). The analysis time was less than 7 min. Prior to MEKC determination, the samples were purified and enriched by carrying out extraction-preconcentration steps. For aqueous samples, off-line SPE with a sorptive material such as Strata-X (polymeric hydrophobic sorbent) and octadecylsilane (C₁₈) was carried out to clean up and preconcentrate the insecticides. However, for soil samples, matrix solid-phase dispersion (MSPD) was applied with C₁₈ used as the dispersant. Good linearity, accuracy, and precision were obtained and the detection limits were in the range between 0.01 and 0.07 μg mL⁻¹ for river water and 0.17 and 0.37 μg g⁻¹ for soil samples. Recovery levels reached greater than 92% for all of the assayed neonicotinoids in river water samples with Strata-X. In soil matrices, the best recoveries (63-99%) were obtained with MSPD. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transport models for desorption from natural soils packed in flushed columns

NASA Astrophysics Data System (ADS)

Brouwers, H. J. H.

1999-06-01

This paper addresses an experimental and theoretical study of sorbed contaminant removal from a column (or reactor) by flushing. This removal may take place by either volatilization or rinsing, and nonlinear sorption is accounted for by employing a Freundlich relationship. A one-dimensional nonequilibrium transport model is proposed which describes the unsteady mass transfer between flushing medium and soil phases in the column, using a linear chemical transfer model. The moving boundary problem is transferred, and a perturbation method is employed to obtain an approximate solution of the governing equations for a small Merkel number Me (this dimensionless number comprises the product of fluid residence time and the mass transfer coefficient). The solution reveals the effect of the various parameters, such as the Freundlich parameter n, on the contaminant transport in fluid phase and decay in solid phase. Applying the model to various experimental data results in values for the overall mass transfer coefficients, which are useful for engineering computations. Furthermore, the model enables the prediction of the initial soil contamination level as well as the parameter n solely from the measured exit contaminant concentrations in the flushing fluid. A thorough comparison of this prediction with the measured soil concentration (prior to the experiments) yields good agreement.

Characteristics of PAH tar oil contaminated soils-Black particles, resins and implications for treatment strategies.

PubMed

Trellu, Clément; Miltner, Anja; Gallo, Rosita; Huguenot, David; van Hullebusch, Eric D; Esposito, Giovanni; Oturan, Mehmet A; Kästner, Matthias

2017-04-05

Tar oil contamination is a major environmental concern due to health impacts of polycyclic aromatic hydrocarbons (PAH) and the difficulty of reaching acceptable remediation end-points. Six tar oil-contaminated soils with different industrial histories were compared to investigate contamination characteristics by black particles. Here we provide a simple method tested on 6 soils to visualize and identify large amounts of black particles (BP) as either solid aggregates of resinified and weathered tar oil or various wood/coke/coal-like materials derived from the contamination history. These materials contain 2-10 times higher PAH concentrations than the average soil and were dominantly found in the sand fraction containing 42-86% of the total PAH. The PAH contamination in the different granulometric fractions was directly proportional to the respective total organic carbon content, since the PAH were associated to the carbonaceous particulate materials. Significantly lower (bio)availability of PAH associated to these carbonaceous phases is widely recognized, thus limiting the efficiency of remediation techniques. We provide a conceptual model of the limited mass transfer of PAH from resinated tar oil phases to the water phase and emphasize the options to physically separate BP based on their lower bulk density and slower settling velocity. Copyright © 2017 Elsevier B.V. All rights reserved.

Enhanced abiotic reduction of Cr(VI) in a soil slurry system by natural biomaterial addition.

PubMed

Park, Donghee; Ahn, Chi Kyu; Kim, Young Mi; Yun, Yeoung-Sang; Park, Jong Moon

2008-12-30

Among various plant-based natural biomaterials, pine bark was chosen as an efficient biomaterial capable of removing toxic Cr(VI) from aqueous solution. XPS spectra indicated that Cr(VI) was abiotically reduced to Cr(III) in both liquid and solid phases. The Cr(VI)-reducing capacity of pine bark was determined as 545 (+/-1.3)mg-Cr(VI)g(-1) of it, which was 8.7 times higher than that of a common chemical Cr(VI)-reductant, FeSO4 x 7H2O. Because pine bark could completely reduce toxic Cr(VI) to less toxic or nontoxic Cr(III) even at neutral pH, it was used as an organic reductant to remediate Cr(VI)-contaminated soil in this study. Soil slurry system using a bottle roller was applied to ex situ slurry-phase remediation experiments. In the soil slurry system, pine bark completely reduced Cr(VI) to Cr(III) and adsorbed the reduced-Cr(III) on its surface. Abiotic remediation rate of Cr(VI)-contaminated soil increased with the increase of pine bark dosage and with the decreases of Cr(VI) and water contents. In conclusion, pine bark can be used to remediate Cr(VI)-contaminated soil efficiently and environmentally friendly.

Selenium speciation in phosphate mine soils and evaluation of a sequential extraction procedure using XAFS.

PubMed

Favorito, Jessica E; Luxton, Todd P; Eick, Matthew J; Grossl, Paul R

2017-10-01

Selenium is a trace element found in western US soils, where ingestion of Se-accumulating plants has resulted in livestock fatalities. Therefore, a reliable understanding of Se speciation and bioavailability is critical for effective mitigation. Sequential extraction procedures (SEP) are often employed to examine Se phases and speciation in contaminated soils but may be limited by experimental conditions. We examined the validity of a SEP using X-ray absorption spectroscopy (XAS) for both whole and a sequence of extracted soils. The sequence included removal of soluble, PO 4 -extractable, carbonate, amorphous Fe-oxide, crystalline Fe-oxide, organic, and residual Se forms. For whole soils, XANES analyses indicated Se(0) and Se(-II) predominated, with lower amounts of Se(IV) present, related to carbonates and Fe-oxides. Oxidized Se species were more elevated and residual/elemental Se was lower than previous SEP results from ICP-AES suggested. For soils from the SEP sequence, XANES results indicated only partial recovery of carbonate, Fe-oxide and organic Se. This suggests Se was incompletely removed during designated extractions, possibly due to lack of mineral solubilization or reagent specificity. Selenium fractions associated with Fe-oxides were reduced in amount or removed after using hydroxylamine HCl for most soils examined. XANES results indicate partial dissolution of solid-phases may occur during extraction processes. This study demonstrates why precautions should be taken to improve the validity of SEPs. Mineralogical and chemical characterizations should be completed prior to SEP implementation to identify extractable phases or mineral components that may influence extraction effectiveness. Sequential extraction procedures can be appropriately tailored for reliable quantification of speciation in contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Quantification of colloidal and aqueous element transfer in soils: The dual-phase mass balance model

USGS Publications Warehouse

Bern, Carleton R.; Thompson, Aaron; Chadwick, Oliver A.

2015-01-01

Mass balance models have become standard tools for characterizing element gains and losses and volumetric change during weathering and soil development. However, they rely on the assumption of complete immobility for an index element such as Ti or Zr. Here we describe a dual-phase mass balance model that eliminates the need for an assumption of immobility and in the process quantifies the contribution of aqueous versus colloidal element transfer. In the model, the high field strength elements Ti and Zr are assumed to be mobile only as suspended solids (colloids) and can therefore be used to distinguish elemental redistribution via colloids from redistribution via dissolved aqueous solutes. Calculations are based upon element concentrations in soil, parent material, and colloids dispersed from soil in the laboratory. We illustrate the utility of this model using a catena in South Africa. Traditional mass balance models systematically distort elemental gains and losses and changes in soil volume in this catena due to significant redistribution of Zr-bearing colloids. Applying the dual-phase model accounts for this colloidal redistribution and we find that the process accounts for a substantial portion of the major element (e.g., Al, Fe and Si) loss from eluvial soil. In addition, we find that in illuvial soils along this catena, gains of colloidal material significantly offset aqueous elemental loss. In other settings, processes such as accumulation of exogenous dust can mimic the geochemical effects of colloid redistribution and we suggest strategies for distinguishing between the two. The movement of clays and colloidal material is a major process in weathering and pedogenesis; the mass balance model presented here is a tool for quantifying effects of that process over time scales of soil development.

Fate and transport of copper-based crop protectants in plasticulture runoff and the impact of sedimentation as a best management practice.

PubMed

Gallagher, D L; Johnston, K M; Dietrich, A M

2001-08-01

The fate and distribution of copper-based crop protectants, applied to plasticulture tomato fields to protect against disease, were investigated in a greenhouse-scale simulation of farming conditions in a coastal environment. Following rainfall, 99% of the applied copper was found to remain on the fields sorbed to the soil and plants; most of the soil-bound copper was found sorbed to the top 2.5 cm of soil between the plasticulture rows. Of the copper leaving the agricultural fields, 82% was found in the runoff with the majority, 74%. sorbed to the suspended solids. The remaining copper, 18%, leached through the soil and entered the groundwater with 10% in the dissolved phase and 8% sorbed to suspended solids. Although only 1% copper was found to leave the field, this was sufficient to cause high copper concentrations (average 2102+/-433 microg/L total copper and 189+/-139 microg/L dissolved copper) in the runoff. Copper concentrations in groundwater samples were also high (average 312+/-198 microg/L total copper and 216+/-99 microg/L dissolved copper). Sedimentation, a best management practice for reducing copper loadings. was found to reduce the total copper concentrations in runoff by 90% to a concentration of 245+/-127 microg/L; however, dissolved copper concentrations remained stable, averaging 139+/-55 microg/L. Total copper concentrations were significantly reduced by the effective removal of suspended solids with sorbed copper.

The relationship between metal toxicity and biotic ligand binding affinities in aquatic and soil organisms: a review.

PubMed

Ardestani, Masoud M; van Straalen, Nico M; van Gestel, Cornelis A M

2014-12-01

The biotic ligand model (BLM) is a theoretical, potentially mechanistic approach to assess metal bioavailability in soil and aquatic systems. In a BLM, toxicity is linked to the fraction of biotic ligand occupied, which in turn, depends on the various components of the solution, including activity of the metal. Bioavailability is a key factor in determining toxicity and uptake of metals in organisms. In this study, the present status of BLM development for soil and aquatic organisms is summarized. For all species and all metals, toxicity was correlated with the conditional biotic ligand binding constants. For almost all organisms, values for Ag, Cu, and Cd were higher than those for Zn and Ni. The constants derived for aquatic systems seem to be equally valid for soil organisms, but in the case of soils, bioavailability from the soil solution is greatly influenced by the presence of the soil solid phase. Copyright © 2014 Elsevier Ltd. All rights reserved.

Assessment of CO2-Induced Geochemical Changes in Soil/Mineral-Water Systems

NASA Astrophysics Data System (ADS)

Jeong, H. Y.; Choi, H. J.

2016-12-01

Although the storage of CO2 in deep geological formations is considered the most promising sequestration path, there is still a risk that it may leak into the atmosphere. To ensure the secure operation of CO2 storage sites, thus, it is necessary to implement CO2 leakage monitoring systems. Furthermore, the leakage may alter geochemical properties of overlying geological units to have adverse environmental consequences. By elucidating geochemical changes due to CO2 leakage, it is possible to develop effective CO2 monitoring techniques and predict the influence of CO2 leakage. A series of batch experiments were conducted to simulate CO2-induced geochemical changes in soil/mineral-water systems. Soil samples, obtained from Eumseong basin in Eumseong-gun, Chungcheongbuk-do, were dried for 6 hours at 60° and then divided into two size fractions: < 106 and 106-212 mm. Minerals including mica/illite, vermiculite, and feldspar were purchased and purified if necessary. Prior to batch experiments, soils and minerals were characterized for surface area, mineralogy, elemental composition, carbon and nitrogen contents, pH buffering capacity, and metal extractability. Batch experiments were initiated by reacting 100% CO2 atmosphere with aqueous suspensions of 120 g soils or 50 g minerals in 3,000 mL of 10 mM CsClO4 at room temperature. In parallel, the batches having the same soil/mineral compositions were run under the ambient air as controls. To prevent microbial activities, all batches were sterilized with 0.03% HCHO. To track geochemical changes, pH and electrical conductivity were monitored. Also, while solutions were regularly sampled and analyzed for trace metals as well as main cations and anions, solid phases were sampled to observe changes in mineralogical compositions. Geochemical changes in both solution and solid phases during the initial 6 month reaction will be presented. Acknowledgement: The "R&D Project on Environmental Management of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003).

Preparation and application of the sol-gel-derived acrylate/silicone co-polymer coatings for headspace solid-phase microextraction of 2-chloroethyl ethyl sulfide in soil.

PubMed

Liu, Mingming; Zeng, Zhaorui; Fang, Huaifang

2005-05-27

Three types of novel acrylate/silicone co-polymer coatings, including co-poly(methyl acrylate/hydroxy-terminated silicone oil) (MA/OH-TSO), co-poly(methyl methacrylate/OH-TSO) (MMA/OH-TSO) and co-poly(butyl methacrylate/OH-TSO) (BMA/OH-TSO), were prepared for the first time by sol-gel method and cross-linking technology and subsequently applied to headspace solid-phase microextraction (HS-SPME) of 2-chloroethyl ethyl sulfide (CEES), a surrogate of mustard, in soil. The underlying mechanisms of the coating process were discussed and confirmed by IR spectra. The selectivity of the three types of sol-gel-derived acrylate/silicone coated fibers was studied, and the BMA/OH-TSO coated fibers exhibited the highest extraction ability to CEES. The concentration of BMA and OH-TSO in sol solution was optimized, and the BMA/OH-TSO (3:1)-coated fibers possessed the highest extraction efficiency. Compared with commercially available polyacrylate (PA) fiber, the sol-gel-derived BMA/OH-TSO (3:1) fibers showed much higher extraction efficiency to CEES. Therefore, the BMA/OH-TSO (3:1)-coated fibers were chosen for the analysis of CEES in soil matrix. The reproducibility of coating preparation was satisfactory, with the RSD 2.39% within batch and 3.52% between batches, respectively. The coatings proved to be quite stable at high temperature (to 350 degrees C) and in different solvents (organic or inorganic), thus their lifetimes (to 150 times) are longer than conventional fibers. Extraction parameters, such as the volume of water added to the soil, extraction temperature and time, and the ionic strength were optimized. The linearity was from 0.1 to 10 microg/g, the limit of detection (LOD) was 2.7 ng/g, and the RSD was 2.19%. The recovery of CEES was 88.06% in agriculture soil, 92.61% in red clay, and 101.95% in sandy soil, respectively.

Simultaneous determination of traces of pyrethroids, organochlorines and other main plant protection agents in agricultural soils by headspace solid-phase microextraction-gas chromatography.

PubMed

Fernandez-Alvarez, Maria; Llompart, Maria; Lamas, J Pablo; Lores, Marta; Garcia-Jares, Carmen; Cela, Rafael; Dagnac, Thierry

2008-04-25

A solvent-free and simple method based on headspace solid-phase microextraction (HS-SPME) was developed in order to determine simultaneously 36 common pesticides and breakdown products (mostly pyrethroids and organochlorine compounds) in soil. The analysis was carried out by gas chromatography with micro-electron-capture detection (GC-microECD). As far as we know, this is the first study about the SPME of pyrethroid insecticides from soil. Factors such as extraction temperature, matrix modification by addition of water, salt addition (% NaCl) and fiber coating were considered in the optimization of the HS-SPME. To this end, a 3 x 2(3-1) fractional factorial design was performed. The results showed that temperature and fiber coating were the most significant variables affecting extraction efficiency. A suitable sensitivity for all investigated compounds was achieved at 100 degrees C by extracting soil samples wetted with 0.5 mL of ultrapure water (0% NaCl) employing a polyacrylate (PA) coating fiber. Using the recommended extraction conditions with GC-microECD, a linear calibration could be achieved over a range of two orders of magnitude for both groups of analytes. Limits of detection (LODS) at the sub-ng g(-1) level were attained and relative standard deviations (RSDs) were found to be lower than 14% for both groups of pesticides. Matrix effects were investigated by the analysis of different soil samples fortified with the target compounds. The method accuracy was assessed and good recovery values (>70%, in most cases) were obtained. The method was also validated with a certified reference material (RTC-CRM818-050), which was quantified using a standard addition protocol. Finally, the proposed HS-SPME-GC-microECD methodology was further applied to the screening of environmental soil samples for the presence of the target pesticides.

Mineralogy and arsenic mobility in arsenic-rich Brazilian soils and sediments

USGS Publications Warehouse

de Mello, J.W.V.; Roy, W.R.; Talbott, J.L.; Stucki, J.W.

2006-01-01

Background. Soils and sediments in certain mining regions of Brazil contain an unusually large amount of arsenic (As), which raises concerns that mining could promote increased As mobility, and thereby increase the risks of contaminating water supplies. Objectives. The purpose of t his study was to identify the most important factors governing As mobility in sediments and soils near three gold-mining sites in the State of Minas Gerais, Brazil. Methods. Surface and sub-surface soil samples were collected at those sites and characterized by chemical and mineralogical analyses. Oxalate (Feo) and citrate-bicarbonate-dithionite (Fed) iron contents were determined by atomic absorption spectroscopy (AAS). Arsenic mobilization was measured after incubating the samples in a 2.5 mM CaCl2 solution under anaerobic conditions for 1, 28, 56, 84, or 112 days. The solution concentrations of As, Fe, and Mn were then measured by inductively coupled plasma-mass spectrometry (ICP-MS) and AAS, respectively. Results and Discussion. Results indicated that As mobilization is largely independent of both the total As and the Feo/Fed ratio of the solid phase. Soluble As is roughly controlled by the Fe (hydr)oxide content of the soil, but a closer examination of the data revealed the importance of other highly weathered clay minerals and organic matter. Large amounts of organic matter and a low iron oxide content should favor As leaching from soils and sediments. Under reducing conditions, As is mobilized by the reductive dissolution of Fe and/or Mn oxides. However, released As may be readsorbed depending on the sorptive properties of the soil. Gibbsite is particularly effective in adsorbing or readsorbing As, as is the remaining unreduced fraction of the iron (hydr)oxides. Conclusion and Outlook. In general, low soluble As is rel ated to the presence of gibbsite, a large amount of iron oxides, and a lack of organic matter in the solid phase. This has environmental significance because gibbsite is thermodynamically more stable than Fe oxides under anaerobic conditions, such as those found in waterlogged soils and lake sediments. ?? 2006 ecomed publishers (Verlagsgruppe Hu??thig Jehle Rehm GmbH), D-86899 Landsberg and Tokyo.

Characterization of organic compounds in biochars derived from municipal solid waste.

PubMed

Taherymoosavi, Sarasadat; Verheyen, Vince; Munroe, Paul; Joseph, Stephen; Reynolds, Alicia

2017-09-01

Municipal solid waste (MSW) generation has been growing in many countries, which has led to numerous environmental problems. Converting MSW into a valuable biochar-based by-product can manage waste and, possibly, improve soil fertility, depending on the soil properties. In this study, MSW-based biochars, collected from domestic waste materials and kerbsides in two Sydney's regions, were composted and pyrolysed at 450°C, 550°C and 650°C. The characteristics of the organic components and their interactions with mineral phases were investigated using a range of analytical techniques, with special attention given to polycyclic aromatic hydrocarbons and heavy metal concentrations. The MSW biochar prepared at 450°C contained the most complex organic compounds. The highest concentration of fixed C, indicating the stability of biochar, was detected in the high-temperature-biochar. Microscopic analysis showed development of pores and migration of mineral phases, mainly Ca/P/O-rich phases, into the micro-pores and Si/Al/O-rich phases on the surface of the biochar in the MSW biochar produced at 550°C. Amalgamation of organic phases with mineral compounds was observed, at higher pyrolysis temperatures, indicating chemical reactions between these two phases at 650°C. XPS analysis showed the main changes occurred in C and N bonds. During heat treatment, N-C/C=N functionalities decomposed and oxidized N configurations, mainly pyridine-N-oxide groups, were formed. The majority of the dissolved organic carbon fraction in both MSW biochar produced at 450°C and 550°C was in the form of building blocks, whereas LMW acids was the main fraction in high-temperature-biochar (59.9%). Copyright © 2017 Elsevier Ltd. All rights reserved.

Utilizing thin-film solid-phase extraction to assess the effect of organic carbon amendments on the bioavailability of DDT and dieldrin to earthworms

USDA-ARS?s Scientific Manuscript database

While DDT and dieldrin have been banned in most countries, contaminated agricultural sites exist in many areas and wildlife exposure is still of concern. Soil was obtained from a historical orchard that received routine pesticide applications more than 40 years ago. Bioavailability of DDT and diel...

Development of supercritical carbon dioxide extraction with a solid phase trap for dioxins in soils and sediments.

PubMed

Miyawaki, Takashi; Kawashima, Ayato; Honda, Katsuhisa

2008-01-01

A method involving supercritical fluid extraction (SFE) with a solid phase trap containing activated alumina was investigated for the rapid analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin like polychlorinated biphenyls (DL-PCBs) in soils and sediments. The samples were extracted by using supercritical carbon dioxide with water (2% versus CO(2) flow velocity) being used as an entrainer at a pressure of 30 MPa and a temperature of 130 degrees C for 50 min. The extracts were adsorbed on an activated alumina trap that was maintained at a temperature of 150 degrees C, and then, PCDD/DFs and DL-PCBs were eluted with 20 ml of hexane at 60 degrees C. After concentration, they were measured with a high-resolution gas chromatograph interfaced to a high-resolution mass spectrometric detector. The average concentrations of PCDD/DFs and DL-PCBs corresponded to the results obtained by the conventional method, and the reproducibility of this SFE method was below 21% of the relative standard deviations for all samples. The total time required for the analysis of the pretreatment of this method was only 2 h.

Biochar affects carbon composition and stability in soil: a combined spectroscopy-microscopy study

PubMed Central

Hernandez-Soriano, Maria C.; Kerré, Bart; Kopittke, Peter M.; Horemans, Benjamin; Smolders, Erik

2016-01-01

The use of biochar can contribute to carbon (C) storage in soil. Upon addition of biochar, there is a spatial reorganization of C within soil particles, but the mechanisms remain unclear. Here, we used Fourier transformed infrared-microscopy and confocal laser scanning microscopy to examine this reorganization. A silty-loam soil was amended with three different organic residues and with the biochar produced from these residues and incubated for 237 d. Soil respiration was lower in biochar-amended soils than in residue-amended soils. Fluorescence analysis of the dissolved organic matter revealed that biochar application increased a humic-like fluorescent component, likely associated with biochar-C in solution. The combined spectroscopy-microscopy approach revealed the accumulation of aromatic-C in discrete spots in the solid-phase of microaggregates and its co-localization with clay minerals for soil amended with raw residue or biochar.The co-localization of aromatic-C:polysaccharides-C was consistently reduced upon biochar application. We conclude that reduced C metabolism is an important mechanism for C stabilization in biochar-amended soils. PMID:27113269

The solonetzic process in surface soils and buried paleosols and its reflection in the mineralogical soil memory

NASA Astrophysics Data System (ADS)

Chizhikova, N. P.; Kovda, I. V.; Borisov, A. V.; Shishlina, N. I.

2009-10-01

The development of the solonetzic process in paleosols buried under kurgans and in the modern surface soils has been studied on the basis of the analysis of the clay (<1 µm) fraction. The revealed changes in the textural differentiation of the soils and the mineralogical composition of the clay fraction during 4500 years are assessed from the viewpoint of the “memory“ of the solid-phase soil components. The mineralogical characteristics show that the solonetzic process in the modern background soil is more developed. The mineralogical approach allows us to reveal the long-term changes in the soil status; it is less useful for studying the effect of short-term bioclimatic fluctuations. In the latter case, more labile soil characteristics should be used. The mineralogical method, combined with other methods, becomes more informative upon the study of soil chronosequences. Our studies have shown that the data on the clay minerals in the buried paleosols may contain specific information useful for paleoreconstructions that is not provided by other methods.

Educational Brief: Using Space for a Better Foundation on Earth Mechanics of Granular Materials

NASA Technical Reports Server (NTRS)

Dooling, Dave (Editor)

2002-01-01

Soils are three-phase composite materials that consist of soil, solid particles, and voids filled with water and/or air. Based on the particle-size distribution, they are generally classified as fine-grained (clays and plastic silts) and coarse-grained soils (nonplastic silts, sand, and gravel). Soil's resistance to external loadings is mainly derived from friction between particles and cohesion. Friction resistance is due to particles' surface-to-surface friction, interlocking, crushing, rearrangement, and dilation (or expansion) during shearing. Cohesion can be due to chemical cementation between particles, electrostatic and electromagnetic forces, and soil-water reaction and equilibrium. The basic factor responsible for the strength of coarse-grained soils is friction. Cohesion can be ignored. This educational brief focuses on measuring shear strength of sands (typical example of coarse-grained soils) where, for the same material, packing density is a main factor to be considered when one asks about the shear strength value. As the external load is applied, the soil's resistance is attained through shearing resistance, which causes the soil volume to increase (expand) or decrease (compress) depending on the initial packing density.

Biochar affects carbon composition and stability in soil: a combined spectroscopy-microscopy study.

PubMed

Hernandez-Soriano, Maria C; Kerré, Bart; Kopittke, Peter M; Horemans, Benjamin; Smolders, Erik

2016-04-26

The use of biochar can contribute to carbon (C) storage in soil. Upon addition of biochar, there is a spatial reorganization of C within soil particles, but the mechanisms remain unclear. Here, we used Fourier transformed infrared-microscopy and confocal laser scanning microscopy to examine this reorganization. A silty-loam soil was amended with three different organic residues and with the biochar produced from these residues and incubated for 237 d. Soil respiration was lower in biochar-amended soils than in residue-amended soils. Fluorescence analysis of the dissolved organic matter revealed that biochar application increased a humic-like fluorescent component, likely associated with biochar-C in solution. The combined spectroscopy-microscopy approach revealed the accumulation of aromatic-C in discrete spots in the solid-phase of microaggregates and its co-localization with clay minerals for soil amended with raw residue or biochar.The co-localization of aromatic-C:polysaccharides-C was consistently reduced upon biochar application. We conclude that reduced C metabolism is an important mechanism for C stabilization in biochar-amended soils.

Biochar affects carbon composition and stability in soil: a combined spectroscopy-microscopy study

NASA Astrophysics Data System (ADS)

Hernandez-Soriano, Maria C.; Kerré, Bart; Kopittke, Peter M.; Horemans, Benjamin; Smolders, Erik

2016-04-01

The use of biochar can contribute to carbon (C) storage in soil. Upon addition of biochar, there is a spatial reorganization of C within soil particles, but the mechanisms remain unclear. Here, we used Fourier transformed infrared-microscopy and confocal laser scanning microscopy to examine this reorganization. A silty-loam soil was amended with three different organic residues and with the biochar produced from these residues and incubated for 237 d. Soil respiration was lower in biochar-amended soils than in residue-amended soils. Fluorescence analysis of the dissolved organic matter revealed that biochar application increased a humic-like fluorescent component, likely associated with biochar-C in solution. The combined spectroscopy-microscopy approach revealed the accumulation of aromatic-C in discrete spots in the solid-phase of microaggregates and its co-localization with clay minerals for soil amended with raw residue or biochar.The co-localization of aromatic-C:polysaccharides-C was consistently reduced upon biochar application. We conclude that reduced C metabolism is an important mechanism for C stabilization in biochar-amended soils.

Separation and quantitation of three acidic herbicide residues in tobacco and soil by dispersive solid-phase extraction and UPLC-MS/MS.

PubMed

Xiong, Wei; Tao, Xiaoqiu; Pang, Su; Yang, Xue; Tang, GangLing; Bian, Zhaoyang

2014-01-01

A method for the determination of three acidic herbicides, dicamba, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in tobacco and soil has been developed based on the use of liquid-liquid extraction and dispersive solid-phase extraction (dispersive-SPE) followed by UPLC-MS/MS. Two percentage of (v/v) formic acid in acetonitrile as the extraction helped partitioning of analytes into the acetonitrile phase. The extract was then cleaned up by dispersive-SPE using primary secondary amine as selective sorbents. Quantitative analysis was done in the multiple-reaction monitoring mode using stable isotope-labeled internal standards for each compound. A separate internal standard for each analyte is required to minimize sample matrix effects on each analyte, which can lead to poor analyte recoveries and decreases in method accuracy and precision. The total analysis time was <4 min. The linear range of the method was from 1 to 100 ng mL(-1) with a limit of detection of each herbicide varied from 0.012 to 0.126 ng g(-1). The proposed method is faster, more sensitive and selective than the traditional methods and more accurate and robust than the published LC-MS/MS methods. © The Author [2013]. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Transfer time and source tracing in the soil - water- -plant system deciphered by the U-and Th-series short-lived nuclides

NASA Astrophysics Data System (ADS)

Rihs, S.; Pierret, M.; Chabaux, F.

2011-12-01

Because soils form at the critical interface between the lithosphere and the atmosphere, characterization of the dynamics occurring through this compartment represents an important goal for several scientific fields and/or human activities. However, this issue remains a challenge because soils are complex systems, where a continuous evolution of minerals and organic soil constituents occurs in response to interactions with waters and vegetation. This study aims to investigate the relevance of short-lived nuclides of U- and Th-series to quantify the transfer times and scheme of radionuclides through a soil - water - plant ecosystem. Activities of (226Ra), (228Ra) and (228Th), as well as the long-lived (232Th), were measured by TIMS and gamma-spectrometry in the major compartments of a forested soil section, i.e.: solid soil fractions (exchangeable fraction, secondary phases and inherited primary minerals), waters (seepage soil waters and a spring further down the watershed) and vegetation (fine and coarse roots of beech trees, young and mature leaves). The matching of these nuclides half-live to bio-geochemical processes time-scale and the relatively good chemical analogy of radium with calcium make these isotopes especially suitable to investigate either time or mechanism of transfers within a soil-water-plant system. Indeed, the (228Ra/226Ra) isotopic ratios strongly differ in the range of samples, allowing quantifying the source and duration transfers. Analyses of the various solid soil fractions demonstrate a full redistribution of Ra isotopes between the inherited minerals and secondary soil phases. However, the transfer of these isotopes to the seepage water or to the tree roots does not follow a simple and obvious scheme. Both primary and secondary phases show to contribute to the dissolved radium. However, depending on the season, the tree leaves degradation also produces up to 70% of dissolved radium. Immobilization of a large part of this radium occurs within the first 70cm of the soil layer, either by plant uptake, or adsorption/ precipitation in particular soil layers. Consistently, the Ra isotope ratio in the spring water is similar to the inherited primary soil fraction, suggesting a "deep" (i.e. below the shallow 70cm of soil layer) origin of the exported dissolved radium and the short-scale effect of vegetation cycling onto radium transfer. The radium isotopic ratio in the trees roots does not match the soil exchangeable fraction, nor the seepage waters, but rather the bulk soil, suggesting a large and mixed pool of radium for roots uptake. Decay of 228Ra within the various parts of the trees allows calculating a vegetation cycling duration of about 10 years for this nuclide. Finally an unexpected large amount of unsupported 228Th in the tree leaves can only be explained by a preferential migration of the 228Ac (228Th precursor). The very short life of this nuclide allows therefore assessing that such transport from roots and deposition within stem and leaves take place within 30 hours at the most.

What is soil organic matter worth?

PubMed

Sparling, G P; Wheeler, D; Vesely, E-T; Schipper, L A

2006-01-01

The conservation and restoration of soil organic matter are often advocated because of the generally beneficial effects on soil attributes for plant growth and crop production. More recently, organic matter has become important as a terrestrial sink and store for C and N. We have attempted to derive a monetary value of soil organic matter for crop production and storage functions in three contrasting New Zealand soil orders (Gley, Melanic, and Granular Soils). Soil chemical and physical characteristics of real-life examples of three pairs of matched soils with low organic matter contents (after long-term continuous cropping for vegetables or maize) or high organic matter content (continuous pasture) were used as input data for a pasture (grass-clover) production model. The differences in pasture dry matter yields (non-irrigated) were calculated for three climate scenarios (wet, dry, and average years) and the yields converted to an equivalent weight and financial value of milk solids. We also estimated the hypothetical value of the C and N sequestered during the recovery phase of the low organic matter content soils assuming trading with C and N credits. For all three soil orders, and for the three climate scenarios, pasture dry matter yields were decreased in the soils with lower organic matter contents. The extra organic matter in the high C soils was estimated to be worth NZ$27 to NZ$150 ha(-1) yr(-1) in terms of increased milk solids production. The decreased yields from the previously cropped soils were predicted to persist for 36 to 125 yr, but with declining effect as organic matter gradually recovered, giving an accumulated loss in pastoral production worth around NZ$518 to NZ$1239 ha(-1). This was 42 to 73 times lower than the hypothetical value of the organic matter as a sequestering agent for C and N, which varied between NZ$22,963 to NZ$90,849 depending on the soil, region, discount rates, and values used for carbon and nitrogen credits.

Assessment of heavy metal contamination in soil due to leachate migration from an open dumping site

NASA Astrophysics Data System (ADS)

Kanmani, S.; Gandhimathi, R.

2013-03-01

The concentration of heavy metals was studied in the soil samples collected around the municipal solid waste (MSW) open dumpsite, Ariyamangalam, Tiruchirappalli, Tamilnadu to understand the heavy metal contamination due to leachate migration from an open dumping site. The dump site receives approximately 400-470 tonnes of municipal solid waste. Solid waste characterization was carried out for the fresh and old municipal solid waste to know the basic composition of solid waste which is dumped in the dumping site. The heavy metal concentration in the municipal solid waste fine fraction and soil samples were analyzed. The heavy metal concentration in the collected soil sample was found in the following order: Mn > Pb > Cu > Cd. The presence of heavy metals in soil sample indicates that there is appreciable contamination of the soil by leachate migration from an open dumping site. However, these pollutants species will continuously migrated and attenuated through the soil strata and after certain period of time they might contaminate the groundwater system if there is no action to be taken to prevent this phenomenon.

Effect of biochar activation by different methods on toxicity of soil contaminated by industrial activity.

PubMed

Kołtowski, Michał; Charmas, Barbara; Skubiszewska-Zięba, Jadwiga; Oleszczuk, Patryk

2017-02-01

The objective of the study was to determine the effect of various methods of biochar activation on the ecotoxicity of soils with various properties and with various content and origin of contaminants. The biochar produced from willow (at 700°C) was activated by 1) microwaves (in a microwave reactor under an atmosphere of water vapour), 2) carbon dioxide (in the quartz fluidized bed reactor) and 3) superheated steam (in the quartz fluidized bed reactor). Three different soils were collected from industrial areas. The soils were mixed with biochar and activated biochars at the dose of 5% and ecotoxicological parameters of mixture was evaluated using two solid phase test - Phytotoxkit F (Lepidium sativum) and Collembolan test (Folsomia candida) and one liquid phase test - Microtox® (Vibrio fischeri). Biochar activation had both positive and negative impacts, depending on the activation method, kind of bioassay and kind of soil. Generally, biochar activated by microwaves increased the effectiveness of ecotoxicity reduction relative to non-activated biochars. Whereas, biochar activated with CO 2 most often cause a negative effect manifested by deterioration or as a lack of improvement in relation to non-activated biochar or to non-amended soil. It was also demonstrated that the increase of biochar specific surface area caused a significant reduction of toxicity of water leachates from the studied soils. Effectiveness of the reduction of leachate toxicity was weakened in the presence of dissolved organic carbon in the soil. Copyright © 2016 Elsevier Inc. All rights reserved.

Full-wave modeling of the time domain reflectometry signal in wetted sandy soils using a random microstructure discretization: Comparison with experiments

NASA Astrophysics Data System (ADS)

Rejiba, F.; Sagnard, F.; Schamper, C.

2011-07-01

Time domain reflectometry (TDR) is a proven, nondestructive method for the measurement of the permittivity and electrical conductivity of soils, using electromagnetic (EM) waves. Standard interpretation of TDR data leads to the estimation of the soil's equivalent electromagnetic properties since the wavelengths associated with the source signal are considerably greater than the microstructure of the soil. The aforementioned approximation tends to hide an important issue: the influence of the microstructure and phase configuration in the generation of a polarized electric field, which is complicated because of the presence of numerous length scales. In this paper, the influence of the microstructural distribution of each phase on the TDR signal has been studied. We propose a two-step EM modeling technique at a microscale range (?): first, we define an equivalent grain including a thin shell of free water, and second, we solve Maxwell's equations over the discretized, statistically distributed triphasic porous medium. Modeling of the TDR probe with the soil sample was performed using a three-dimensional finite difference time domain scheme. The effectiveness of this hybrid homogenization approach is tested on unsaturated Nemours sand with narrow granulometric fractions. The comparisons made between numerical and experimental results are promising, despite significant assumptions concerning (1) the TDR probe head and the coaxial cable and (2) the assumed effective medium theory homogenization associated with the electromagnetic processes arising locally between the liquid and solid phases at the grain scale.

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano.

PubMed

Floor, Geerke H; Iglesías, Mònica; Román-Ross, Gabriela; Corvini, Philippe F X; Lenz, Markus

2011-09-01

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH<4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L(-1) using (78)Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H(2)SO(4) and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments. Copyright © 2011 Elsevier Ltd. All rights reserved.

Influence of solid dairy manure and compost with and without alum on survival of indicator bacteria in soil and on potato.

PubMed

Entry, James A; Leytem, April B; Verwey, Sheryl

2005-11-01

We measured Escherichia coli, Enterococcus spp. and fecal coliform numbers in soil and on fresh potato skins after addition of solid dairy manure and dairy compost with and without alum (Al(2)(SO(4))(3)) treatment 1, 7, 14, 28, 179 and 297 days after application. The addition of dairy compost or solid dairy manure at rates to meet crop phosphorus uptake did not consistently increase E. coli and Enterococcus spp. and fecal coliform bacteria in the soil. We did not detect E. coli in any soil sample after the first sampling day. Seven, 14, 28, 179 and 297 days after solid dairy waste and compost and alum were applied to soil, alum did not consistently affect Enterococcus spp. and fecal coliform bacteria in the soil. We did not detect E. coli in any soil, fresh potato skin or potato wash-water at 214 days after dairy manure or compost application regardless of alum treatment. Dairy compost or solid dairy manure application to soil at rates to meet crop phosphorus uptake did not consistently increase Enterococcus spp. and fecal coliform numbers in bulk soil. Solid dairy manure application to soil at rates to meet crop phosphorus uptake, increased Enterococcus spp. and fecal coliform numbers in potato rhizosphere soil. However, fresh potato skins had higher Enterococcus spp. and fecal coliform numbers when solid dairy manure was added to soil compared to compost, N and P inorganic fertilizer and N fertilizer treatments. We did not find any E. coli, Enterococcus or total coliform bacteria on the exterior of the tuber, within the peel or within a whole baked potato after microwave cooking for 5 min.

Comparison of solid-phase bioassays and ecoscores to evaluate the toxicity of contaminated soils.

PubMed

Lors, Christine; Ponge, Jean-François; Martínez Aldaya, Maite; Damidot, Denis

2010-08-01

Five bioassays (inhibition of lettuce germination and growth, earthworm mortality, inhibition of springtail population growth, avoidance by springtails) were compared, using four coke factory soils contaminated by PAHs and trace elements, before and after biotreatment. For each bioassay, several endpoints were combined in an 'ecoscore', a measure of test sensitivity. Ecoscores pooled over all tested bioassays revealed that most organisms were highly sensitive to the concentration of 3-ring PAHs. When four soils were combined, behavioural tests using the springtail Folsomia candida showed higher ecoscores, i.e. they were most sensitive to soil contamination. However, despite overall higher sensitivity of behavioural tests, which could be used for cheap and rapid assessment of soil toxicity, especially at low levels of contamination, some test endpoints were more sensitive than others, and this may differ from a soil to another, pointing to the need for a battery of bioassays when more itemized results are expected. Copyright 2010 Elsevier Ltd. All rights reserved.

Development of a multi-residue enantiomeric analysis method for 9 pesticides in soil and water by chiral liquid chromatography/tandem mass spectrometry.

PubMed

Li, Yuanbo; Dong, Fengshou; Liu, Xingang; Xu, Jun; Chen, Xiu; Han, Yongtao; Liang, Xuyang; Zheng, Yongquan

2013-04-15

A novel and sensitive chiral liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method was developed and validated for simultaneous measuring individual enantiomers of 9 pesticides including herbicides, insecticides, and fungicides in soil and water. The separation and determination were performed using reversed-phase chromatography on an amylose chiral stationary phase, a Chiralpak AD-RH column, under gradient elution using a mixture of ACN-2mM ammonium acetate in water as the mobile phase at 0.45 mL/min flow rate. The effects of three cellulose-based columns and three amylose-based columns on the separation were also investigated. The QuEChERS (acronym for Quick, Easy, Cheap, Effective, Rugged and Safe) method and solid-phase extraction (SPE) were used for the extraction and clean-up of the soil and water samples, respectively. Parameters including the matrix effect, linearity, precision, accuracy and stability were undertaken. Under optimal conditions, the mean recoveries for all enantiomers from the soil and water samples were ranged from 77.8% to 106.2% with the relative standard deviations (RSD) less than 14.2%. Good linearity (at least R(2) ≥ 0.9986) was obtained for all studied analytes in the soil and water matrix calibration curves over the range from 2.0 to 125 μg/L. The limits of detection (LOD) for all enantiomers in the soil and water were less than 1.8 μg/kg or μg/L, whereas the limit of quantification (LOQ) did not exceed 5.0 μg/kg or μg/L. The results of the method validation confirm that this proposed method is convenient and reliable for the enantioselective determination of the enantiomers of 9 chiral pesticides in soil and water. Copyright © 2013 Elsevier B.V. All rights reserved.

Pig slurry acidification and separation techniques affect soil N and C turnover and N2O emissions from solid, liquid and biochar fractions.

PubMed

Gómez-Muñoz, B; Case, S D C; Jensen, L S

2016-03-01

The combined effects of pig slurry acidification, subsequent separation techniques and biochar production from the solid fraction on N mineralisation and N2O and CO2 emissions in soil were investigated in an incubation experiment. Acidification of pig slurry increased N availability from the separated solid fractions in soil, but did not affect N2O and CO2 emissions. However acidification reduced soil N and C turnover from the liquid fraction. The use of more advanced separation techniques (flocculation and drainage > decanting centrifuge > screw press) increased N mineralisation from acidified solid fractions, but also increased N2O and CO2 emissions in soil amended with the liquid fraction. Finally, the biochar production from the solid fraction of pig slurry resulted in a very recalcitrant material, which reduced N and C mineralisation in soil compared to the raw solid fractions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Simple method for the determination of personal care product ingredients in lettuce by ultrasound-assisted extraction combined with solid-phase microextraction followed by GC-MS.

PubMed

Cabrera-Peralta, Jerónimo; Peña-Alvarez, Araceli

2018-05-01

A simple method for the simultaneous determination of personal care product ingredients: galaxolide, tonalide, oxybenzone, 4-methylbenzyliden camphor, padimate-o, 2-ethylhexyl methoxycinnamate, octocrylene, triclosan, and methyl triclosan in lettuce by ultrasound-assisted extraction combined with solid-phase microextraction followed by gas chromatography with mass spectrometry was developed. Lettuce was directly extracted by ultrasound-assisted extraction with methanol, this extract was combined with water, extracted by solid-phase microextraction in immersion mode, and analyzed by gas chromatography with mass spectrometry. Good linear relationships (25-250 ng/g, R 2  > 0.9702) and low detection limits (1.0-25 ng/g) were obtained for analytes along with acceptable precision for almost all analytes (RSDs < 20%). The validated method was applied for the determination of personal care product ingredients in commercial lettuce and lettuces grown in soil and irrigated with the analytes, identifying the target analytes in leaves and roots of the latter. This procedure is a miniaturized and environmentally friendly proposal which can be a useful tool for quality analysis in lettuce. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preconcentration and separation of nickel, copper and cobalt using solid phase extraction and their determination in some real samples.

PubMed

Ghaedi, M; Ahmadi, F; Soylak, M

2007-08-17

A solid phase extraction method has been developed to separate and concentrate trace amounts of nickel, cobalt and copper ions from aqueous samples for the measurement by flame atomic absorption spectrometry. By the passage of aqueous samples through activated carbon modified by dithioxamide (rubeanic acid) (DTO), Ni2+, Cu2+ and Co2+ ions adsorb quantitatively. The recoveries of analytes at pH 5.5 with 500 mg solid phase were greater than 95% without interference from alkaline, earth alkaline and some metal ions. The enrichment factor was 330. The detection limits by three sigma were 0.50 microg L(-1) for copper, 0.75 microg L(-1) for nickel and 0.80 microg L(-1) for cobalt. The loading capacity was 0.56 mg g(-1) for Ni2+, 0.50 mg g(-1) for Cu2+ and 0.47 mg g(-1) for Co2+. The presented procedure was applied to the determination of analytes in tap, river and sea waters, vegetable, soil and blood samples with successfully results (recoveries greater than 95%, R.S.D. lower than 2% for n=3).

Occurrence of veterinary antibiotics and progesterone in broiler manure and agricultural soil in Malaysia.

PubMed

Ho, Yu Bin; Zakaria, Mohamad Pauzi; Latif, Puziah Abdul; Saari, Nazamid

2014-08-01

Repeated applications of animal manure as fertilizer are normal agricultural practices that may release veterinary antibiotics and hormones into the environment from treated animals. Broiler manure samples and their respective manure-amended agricultural soil samples were collected in selected locations in the states of Selangor, Negeri Sembilan and Melaka in Malaysia to identify and quantify veterinary antibiotic and hormone residues in the environment. The samples were analyzed using ultrasonic extraction followed by solid phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The broiler manure samples were found to be contaminated with at least six target analytes, namely, doxycycline, enrofloxacin, flumequine, norfloxacin, trimethoprim and tylosin. These analytes were detected in broiler manure samples with maximum concentrations reaching up to 78,516 μg kg(-1) dry weight (DW) (doxycycline). For manure-amended agricultural soil samples, doxycycline and enrofloxacin residues were detected in every soil sample. The maximum concentration of antibiotic detected in soil was 1331 μg kg(-1) DW (flumequine). The occurrence of antibiotics and hormones in animal manure at high concentration poses a risk of contaminating agricultural soil via fertilization with animal manure. Some physico-chemical parameters such as pH, total organic carbon (TOC) and metal content played a considerable role in the fate of the target veterinary antibiotics and progesterone in the environment. It was suggested that these parameters can affect the adsorption of pharmaceuticals to solid environmental matrices. Copyright © 2014 Elsevier B.V. All rights reserved.

Chemical-Specific Representation of Air-Soil Exchange and Soil Penetration in Regional Multimedia Models

DOE Office of Scientific and Technical Information (OSTI.GOV)

McKone, T.E.; Bennett, D.H.

2002-08-01

In multimedia mass-balance models, the soil compartment is an important sink as well as a conduit for transfers to vegetation and shallow groundwater. Here a novel approach for constructing soil transport algorithms for multimedia fate models is developed and evaluated. The resulting algorithms account for diffusion in gas and liquid components; advection in gas, liquid, or solid phases; and multiple transformation processes. They also provide an explicit quantification of the characteristic soil penetration depth. We construct a compartment model using three and four soil layers to replicate with high reliability the flux and mass distribution obtained from the exact analyticalmore » solution describing the transient dispersion, advection, and transformation of chemicals in soil with fixed properties and boundary conditions. Unlike the analytical solution, which requires fixed boundary conditions, the soil compartment algorithms can be dynamically linked to other compartments (air, vegetation, ground water, surface water) in multimedia fate models. We demonstrate and evaluate the performance of the algorithms in a model with applications to benzene, benzo(a)pyrene, MTBE, TCDD, and tritium.« less

Extension of coupled multispecies metal transport and speciation (TRANSPEC) model to soil.

PubMed

Bhavsar, Satyendra P; Gandhi, Nilima; Diamond, Miriam L

2008-01-01

Atmospheric deposition of metals emitted from mining operations has raised metal concentrations in the surrounding soils. This repository may be remobilized and act as a source of metals to nearby surface aquatic systems. It is important to understand metal dynamics and the impact of various chemistry and fate parameters on metal movement in the soil environment in order to evaluate risk associated with metals in terrestrial ecosystems and accurately establish critical discharge limits that are protective of aquatic biota. Here we extend our previously developed coupled multispecies metal fate-TRANsport and SPECiation/complexation (TRANSPEC) model, which was applicable to surface aquatic systems. The extended TRANSPEC, termed TRANSPEC-II, estimates the partition coefficient, K(d), between the soil-solid and -soluble phases using site-specific data and a semi-empirical regression model obtained from literature. A geochemical model calculates metal and species fractions in the dissolved and colloidal phases of the soil solution. The multispecies fugacity/aquivalence based fate-transport model then estimates inter-media transport rates such as leaching from soil, soil runoff, and water-sediment exchanges of each metal species. The model is illustratively applied to Ni in the Kelly Lake watershed (Sudbury, Ontario, Canada), where several mining operations are located. The model results suggest that the current atmospheric fallout supplies only 4% of Ni removed from soil through soil runoff and leaching. Soil runoff contributes about 20% of Ni entering into Kelly Lake with the rest coming from other sources. Leaching to groundwater, apart from runoff, is also a major loss process for Ni in the soil. A sensitivity analysis indicates that raising soil pH to above 6 may substantially reduce metal runoff and improve water quality of nearby water bodies that are impacted by runoff.

Theoretical and numerical aspects of fluid-saturated elasto-plastic soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ehlers, W.

1995-12-31

The theoretical and numerical treatment of fluid-saturated porous solid materials generally falls into the category of porous media models, which are described within the framework of the classical theory of mixtures extended by the concept of volume fractions (porous media theories). In particular, this concept allows for the description of saturated, unsaturated and empty porous matrix materials, thus offering a well-founded theoretical background for a lot of engineering problems occurring, for instance, in the fields of geomechanics (soil and rock mechanics as well as glacier and rock ice mechanics), oil producing industries, sintering technologies, biomechanics, etc. In the present contribution,more » theoretical and numerical studies are outlined to describe a two-phase material composed of an incompressible elasto-plastic soil matrix saturated by an incompressible viscous pore fluid. In this context, the phenomenon of phase incompressibility is well known as a microscopic effect not implying bulk incompressibility in the macro regime. This is seen from the fact that even if the material density functions of the individual constituents are constant during deformation, the corresponding bulk densities can still change through changes in the volume fractions. Within the framework of a pure mechanical theory, constitutive equations are given for both the solid and the fluid partial stress tensors and for the interaction force acting between the two materials. Concerning the porous soil matrix, the elastic properties are described by an elasticity law of Hookean type, while the plastic range is governed by a {open_quote}single surface{close_quote} yield function exhibiting a smooth and closed shape in the principal stress space together with a non-associated flow rule. The viscosity effects of the pore fluid are included in the fluid stress tensor and in the drag force.« less

Preparation and utilization of molecularly imprinted polymer for chlorsulfuron extraction from water, soil, and wheat plant.

PubMed

Fu, Xu Wei; Wu, Yan Jiao; Qu, Jin Rong; Yang, Hong

2012-07-01

A molecularly imprinted polymer (MIP) was prepared using chlorsulfuron (CS), a herbicide as a template molecule, methacrylic acid as a functional monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linker, methanol and toluene as a porogen, and 2,2-azobisisobutyronitrile as an initiator. The binding behaviors of the template chlorsulfuron and its analog on MIP were evaluated by equilibrium adsorption experiments, which showed that the MIP particles had specific affinity for the template CS. Solid-phase extraction (SPE) with the chlorsulfuron molecularly imprinted polymer as an adsorbent was investigated. The optimum loading, washing, and eluting conditions for chlorsulfuron molecularly imprinted polymer solid-phase extraction (CS-MISPE) were established. The optimized CS-MISPE procedure was developed to enrich and clean up the chlorsulfuron residue in water, soils, and wheat plants. Concentrations of chlorsulfuron in the samples were analyzed by HPLC-UVD. The average recoveries of CS spiked standard at 0.05~0.2 mg L(-1) in water were 90.2~93.3%, with the relative standard deviation (RSD) being 2.0~3.9% (n=3). The average recoveries of 1.0 mL CS spiked standard at 0.1~0.5 mg L(-1) in 10 g soil were 91.1~94.7%, with the RSD being 3.1~5.6% (n=3). The average recoveries of 1.0 mL CS spiked standard at 0.1~0.5 mg L(-1) in 5 g wheat plant were 82.3~94.3%, with the RSD being 2.9~6.8% (n=3). Overall, our study provides a sensitive and cost-effective method for accurate determination of CS residues in water, soils, and plants.

Novel approach to microwave-assisted extraction and micro-solid-phase extraction from soil using graphite fibers as sorbent.

PubMed

Xu, Li; Lee, Hian Kee

2008-05-30

A single-step extraction-cleanup procedure involving microwave-assisted extraction (MAE) and micro-solid-phase extraction (micro-SPE) has been developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) from soil samples. Micro-SPE is a relatively new extraction procedure that makes use of a sorbent enclosed within a sealed polypropylene membrane envelope. In the present work, for the first time, graphite fiber was used as a sorbent material for extraction. MAE-micro-SPE was used to cleanup sediment samples and to extract and preconcentrate five PAHs in sediment samples prepared as slurries with addition of water. The best extraction conditions comprised of microwave heating at 50 degrees C for a duration of 20 min, and an elution (desorption) time of 5 min using acetonitrile with sonication. Using gas chromatography (GC)-flame ionization detection (FID), the limits of detection (LODs) of the PAHs ranged between 2.2 and 3.6 ng/g. With GC-mass spectrometry (MS), LODs were between 0.0017 and 0.0057 ng/g. The linear ranges were between 0.1 and 50 or 100 microg/g for GC-FID analysis, and 1 and 500 or 1000 ng/g for GC-MS analysis. Granular activated carbon was also used for the micro-SPE device but was found to be not as efficient in the PAH extraction. The MAE-micro-SPE method was successfully used for the extraction of PAHs in river and marine sediments, demonstrating its applicability to real environmental solid matrixes.

Ultra-high-pressure liquid chromatography-tandem mass spectrometry method for the determination of alkylphenols in soil.

PubMed

Wang, Jing; Pan, Hefang; Liu, Zhengzheng; Ge, Fei

2009-03-20

A novel method has been developed for the determination of alkylphenols in soil by ultra-high-pressure liquid chromatography employing small particle sizes, combined with tandem mass spectrometry. Soil samples were extracted with pressurized liquid extraction (PLE) and then cleaned with solid-phase extraction (SPE). The extracts were separated on C18 column (1.7 microm, 50 mm x 2.1mm) with a gradient elution and a mobile phase consisting of water and acetonitrile, and then detected by an electrospray ionization tandem mass spectrometry in negative ion mode with multiple reaction monitoring (MRM). Compared with traditional liquid chromatography, it took ultra-high-pressure liquid chromatography much less time to analyze alkylphenols. Additionally, the ultra-high-pressure liquid chromatography/tandem mass spectrometry method produces satisfactory reliability, sensitivity, and accuracy. The average recoveries of the three target analytes were 74.0-103.4%, with the RSD<15%. The calibration curves for alkylphenols were linear within the range of 0.01-0.4 microg/ml, with the correlation coefficients greater than 0.99. When 10 g soil sample was used for analysis, the limits of quantification (LOQs) of the three alkylphenols were all 1.0 microg/kg.

Application and validation of isotope dilution method (IDM) for predicting bioavailability of hydrophobic organic contaminants in soil.

PubMed

Wang, Jie; Taylor, Allison; Schlenk, Daniel; Gan, Jay

2018-05-01

Risk assessment of hydrophobic organic contaminants (HOCs) using the total chemical concentration following exhaustive extraction may overestimate the actual availability of HOCs to non-target organisms. Existing methods for estimating HOC bioavailability in soil have various operational limitations. In this study, we explored the application of isotope dilution method (IDM) to quantify the accessible fraction (E) of DDTs and PCBs in both historically-contaminated and freshly-spiked soils. After addition of 13 C or deuterated analogues to a soil sample, the phase distribution of isotope-labeled and native chemicals reached an apparent equilibrium within 48 h of mixing. The derived E values in the three soils ranged from 0.19 to 0.82, depending on the soil properties and also the contact time of HOCs (i.e., aging). The isotope dilution method consistently predicted greater accumulation into earthworm (Eisenia fetida) than that by polyethylene (PE) or solid phase microextraction (SPME) sampler, likely because desorption in the gut enhanced bioavailability of soil-borne HOCs. A highly significant linear regression (R 2  = 0.91) was found between IDM and 24-h Tenax desorption, with a slope statistically identical to 1. The IDM-derived accessible concentration (C e ) was further shown to accurately predict tissue residues in earthworm exposed in the same soils. Given the relatively short duration and simple steps, IDM has the potential to be readily adopted for measuring HOC bioaccessibility in soil and for improving risk assessment and evaluation of remediation efficiency. Copyright © 2018 Elsevier Ltd. All rights reserved.

Important aspects in the formulation of solid-fluid debris-flow models. Part I. Thermodynamic implications

NASA Astrophysics Data System (ADS)

Hutter, Kolumban; Schneider, Lukas

2010-06-01

This article points at some critical issues which are connected with the theoretical formulation of the thermodynamics of solid-fluid mixtures of frictional materials. It is our view that a complete thermodynamic exploitation of the second law of thermodynamics is necessary to obtain the proper parameterizations of the constitutive quantities in such theories. These issues are explained in detail in a recently published book by Schneider and Hutter (Solid-Fluid Mixtures of Frictional Materials in Geophysical and Geotechnical Context, 2009), which we wish to advertize with these notes. The model is a saturated mixture of an arbitrary number of solid and fluid constituents which may be compressible or density preserving, which exhibit visco-frictional (visco-hypoplastic) behavior, but are all subject to the same temperature. Mass exchange between the constituents may account for particle size separation and phase changes due to fragmentation and abrasion. Destabilization of a saturated soil mass from the pre- and the post-critical phases of a catastrophic motion from initiation to deposition is modeled by symmetric tensorial variables which are related to the rate independent parts of the constituent stress tensors.

Novel Insight for Organic Matter Sourcing: Interest of Time Resolved Fluorescence to Qualify and Quantify PAH Content of Solid Matrix at High Resolution

NASA Astrophysics Data System (ADS)

Quiers, M.; Perrette, Y.; Jacq, K.; Pousset, E.; Plassart, G.

2017-12-01

OM fluorescence is today a well-developed tool used to characterize and quantify organic matter (OM), but also to evaluate and discriminate OM fate and changes related to climate and environmental modifications. While fluorescence measurements on water and soils extracts provide information about organic fluxes today, solid phase fluorescence using natural archives allows to obtain high resolution records of OM evolution during time. These evolutions can be discussed in regards of climate and environmental perturbations detected in archives using different proxies, and thus provide keys for understanding factors driving carbon fluxes mechanisms. Among fluorescent organic species, Polycyclic Aromatic Hydrocarbons (PAH) have been used as probe molecules for organic contamination tracking. Moreover, monitoring studies have shown that PAH could also be used as markers to discriminates atmospheric and erosion factors leading to PAH and organic matter fluxes to the aquifer. PAH records in soils and natural archives appear as a promising proxy to follow both past atmospheric contamination and soil erosion. But, PAH fluorescence is difficult to discriminate from bulk OM fluorescence using steady-state fluorescence (SSF) technics as their fluorescence domains recover. Time resolved emission spectroscopy (TRES) increases the information provided by SSF technic, adding a time dimension to measurements and allowing to discriminate PAH fluorescence. We report here a first application of this technic on natural archives. The challenge is to obtain TRES signature along the sample, including for low PAH concentrations. This study aims to evaluate the reliability of high resolution TRES measurement as PAH carbon fluxes sources. Method is based on LIF instrument for solid phase fluorescence measurement. An instrument coupling an excitation system constituting by 2 pulsed lasers (266 and 355 nm) and a detection system was developed. This measurement provides high resolution record of PAH fluorescence. Preliminary results on stalagmite samples, lake sediments and soils will be reported. PAH content variations along the sample were compared with PAH concentration and with bulk OM content deduced from SSF records. The accuracy of the PAH fluorescence as source marker of fluxes will be discussed for each type of sample.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Distler, T. M.; Wong, C. M.

Runoff-water samples for the first, third, and fourth quarters of 1975 were analyzed for pesticide residues at LLL and independently by the LFE Environmental Analysis Laboratories. For the compounds analyzed, upper limits to possible contamination were placed conservatively at the low parts-per-billion level. In addition, soil samples were also analyzed. Future work will continue to include quarterly sampling and will be broadened in scope to include quantitative analysis of a larger number of compounds. A study of recovery efficiency is planned. Because of the high backgrounds on soil samples together with the uncertainties introduced by the cleanup procedures, there ismore » little hope of evaluating the distribution of a complex mixture of pesticides among the aqueous and solid phases in a drainage sample. No further sampling of soil from the streambed is therefore contemplated.« less

Development of an analytical procedure to study linear alkylbenzenesulphonate (LAS) degradation in sewage sludge-amended soils.

PubMed

Comellas, L; Portillo, J L; Vaquero, M T

1993-12-24

A procedure for determining linear alkylbenzenesulphonates (LASs) in sewage sludge and amended soils has been developed. Extraction by sample treatment with 0.5 M potassium hydroxide in methanol and reflux was compared with a previously described extraction procedure in Soxhlet with methanol and solid sodium hydroxide in the sample. Repeatability results were similar with savings in extraction time, solvents and evaporation time. A clean-up method involving a C18 cartridge has been developed. Analytes were quantified by a reversed-phase HPLC method with UV and fluorescence detectors. Recoveries obtained were higher than 84%. The standing procedure was applied to high doses of sewage sludge-amended soils (15%) with increasing quantities of added LASs. Degradation data for a 116-day period are presented.

Tungsten Speciation and Solubility in Munitions-Impacted Soils.

PubMed

Bostick, Benjamín C; Sun, Jing; Landis, Joshua D; Clausen, Jay L

2018-02-06

Considerable questions persist regarding tungsten geochemistry in natural systems, including which forms of tungsten are found in soils and how adsorption regulates dissolved tungsten concentrations. In this study, we examine tungsten speciation and solubility in a series of soils at firing ranges in which tungsten rounds were used. The metallic, mineral, and adsorbed forms of tungsten were characterized using X-ray absorption spectroscopy and X-ray microprobe, and desorption isotherms for tungsten in these soils were used to characterize its solid-solution partitioning behavior. Data revealed the complete and rapid oxidation of tungsten metal to hexavalent tungsten(VI) and the prevalence of adsorbed polymeric tungstates in the soils rather than discrete mineral phases. These polymeric complexes were only weakly retained in the soils, and porewaters in equilibrium with contaminated soils had 850 mg L -1 tungsten, considerably in excess of predicted solubility. We attribute the high solubility and limited adsorption of tungsten to the formation of polyoxometalates such as W 12 SiO 40 4- , an α-Keggin cluster, in soil solutions. Although more research is needed to confirm which of such polyoxometalates are present in soils, their formation may not only increase the solubility of tungsten but also facilitate its transport and influence its toxicity.

Soils as records of past and present environments

NASA Astrophysics Data System (ADS)

Sauer, Daniela

2015-04-01

This contribution reflects selected pedological concepts that are helpful for interpreting soil properties related to past and present environments. These concepts are illustrated by examples from various landscapes, and their combination finally leads to some further conclusions. The concept of Targulian and Gerasimova (2009) distinguishes soil system and soil body. Soil system is defined as "open multiphase system functioning in any solid-phase substrate at its interface with the atmosphere, hydrosphere and biota", and soil body as "solid-phase part of a soil system produced by its long-term functioning and composed of a vertical sequence of genetic horizons". Soil system functioning corresponds to the recent environmental factors and includes heat and moisture dynamics, biomass production, biogeochemical cycles, and other processes. In contrast, a soil body is a record of the long-term functioning of a soil system. It thus provides a record not only of the functioning of the soil system under the present environmental conditions but also under past, possibly different, conditions. Hence, Targulian and Goryachkin (2004) called it the "memory" of the landscape. Richter and Yaalon (2012) argued that most soils comprise both, features that developed under the present environmental conditions and features that reflect different conditions that the soils experienced in the past; they concluded that most soils are polygenetic. Although the current functioning of the soil system in the concept of Targulian and Gerasimova (2009) is mainly controlled by the present-day combination of environmental factors, it should be added that past processes also influence the soil system, because past processes changed the soil properties in a way that also the present-day functioning of the soil system is affected by these changes. Earlier, Yaalon (1971) had categorised soil properties according to the time-span required for their adjustment to the actual environment, distinguishing (i) rapidly adjusting soil properties (adjusting within some hundreds of years), (ii) slowly adjusting soil properties (adjusting within some thousands of years), and (iii) persistent soil properties (showing no changes over ten thousands to millions of years). In a polygenetic soil, rapidly adjusting soil properties may already be in equilibrium with the present conditions, whereas slowly adjusting soil properties may still reflect past conditions. Thus, the lower the rate at which a certain soil property in a polygenetic soil adjusts, the larger is the extent to which this property is still determined by earlier environmental conditions. Knowledge on the rates at which soil properties adjust may hence be used to estimate the time at which a significant environmental change took place, based on the degree of overprinting of the different kinds of soil properties adjusting at different rates in a polygenetic soil. References: Richter, D. de B., Yaalon, D.H., 2012. "The changing model of soil" revisited. Soil Sci. Soc. Am. J. 76, 766-778. Targulian, V. O., Goryachkin, S. V., 2004. Soil memory: Types of records, carriers, hierarchy and diversity. Revista Mexicana Ciencias Geol. 21, 1-8. Targulian, V.O., Gerasimova, M., 2009. Soil geography: geography of soil systems and soil bodies. Soil Geography: New Horizons. International Conference, 16-20 November 2009 in Huatulco, Mexico. Book of abstracts, 39. Yaalon, D.H., 1971. Soil forming processes in time and space. In: Yaalon, D.H. (Ed.), Paleopedology-origin, nature and dating of paleosols. Int. Soc. Soil Sci. and Israel Univ. Press, Jerusalem, pp. 29-39.

On the location of acid-hydrolysable carbon in lunar soil fines

NASA Technical Reports Server (NTRS)

Fallick, A. E.; Wright, I. P.; Pillinger, C. T.; Stephenson, A.; Morris, R. V.

1982-01-01

Soil fines exposed on the lunar surface accumulate small metallic iron particles and solar wind-derived carbon. In previous work, it has been suggested that an intimate association exists between one particular carbon phase, hydrolysable carbon, and very fine iron droplets, where the carbon is in solid solution in the iron. The earlier hypothesis of a constant carbon in iron concentration across a broad range of droplet sizes is testable by combining hydrolysable carbon determinations with a variety of magnetic measurements sensitive to different droplet diameters. New measurements of ferromagnetic resonance response on density and magnetic separates from size fractions of soil 12023 are interpreted as evidence that hydrolysable carbon is preferentially associated with the larger, magnetically stable single-domain iron particles rather than with the smaller superparamagnetic droplets. For the former, there is a quite uniform ratio of iron to carbon both within a series of separates from a single soil, and among soils of widely varying FeO content.

Solid phase extraction of metal ions in environmental samples on 1-(2-pyridylazo)-2-naphthol impregnated activated carbon cloth.

PubMed

Alothman, Zeid A; Yilmaz, Erkan; Habila, Mohamed; Soylak, Mustafa

2015-02-01

1-(2-Pyridylazo)-2-naphthol impregnated activated carbon cloth (PAN-imp-ACC) was prepared as a solid phase sorbent and, for the first time, was used for the simultaneous separation and preconcentration of trace amounts of lead, cadmium and nickel in water, soil and sewage sludge samples prior to determination by flame atomic absorption spectrometry (FAAS). The parameters governing the efficiency of the method were optimized, including the pH, the eluent type and volume, the sample and eluent flow rates, diverse ions effects and the sample volume. A preconcentration factor of 100 was achieved for all the metal ions, with detection limits of 0.1-2.8 µg L(-1) and relative standard deviations below 6.3%. The adsorption capacity of the PAN-imp-ACC for Pb(II), Cd(II) and Ni(II) ions was found to be 45.0 mg g(-1), 45.0 mg g(-1) and 43.2 mg g(-1), respectively. The method was validated by the analysis of the certified reference materials TMDA-64.2 fortified Lake Ontario water and BCR-146R Sewage Sludge Amended Soil (Industrial Origin). The procedure was applied to determine the analytes content in real samples. Copyright © 2014 Elsevier Inc. All rights reserved.

A new methodology involving stable isotope tracer to compare short- and long- term selenium mobility in soils

NASA Astrophysics Data System (ADS)

Tolu, Julie; Thiry, Yves; Potin-gautier, Martine; Le hécho, Isabelle; Bueno, Maïté

2013-04-01

Selenium is an element of environmental concern given its dual beneficial and toxic character to animal and human health. Its radioactive isotope 79Se, a fission product of 235U, is considered critical in safety assessment of nuclear waste repositories in case of leakage and hypothetical soil contamination. Therefore, Se species transformations and interactions with soil components have to be clearly understood to predict its dispersion in the biosphere (e.g., accumulation in soils, migration to waters, transfer to living organisms). While natural Se interactions with soils run over centuries to millennia time scales, transformations and partitioning are generally studied with short-term experiments (often inferior to 1 month) after Se addition. The influence of slower, long-term processes involved in Se speciation and mobility in soils is thus not properly accounted for. We tested if using ambient Se would be relevant for long-term risk assessment while added Se would be more representative of short-term contamination impact. For that purpose, we developed a new methodology to trace the differential reactivity of ambient and spiked Se at trace level (µg kg-1) in soils. It combined the use of a stable isotopically enriched tracer with our previous published analytical method based on specific extractions and HPLC-ICP-MS to determine trace Se species partition in different soil phases. Given that soil extracts contains very high concentrations of various elements interfering Se (e.g., Fe, Cl, Br), the ICP-MS parameters and mathematical corrections were optimized to cope with such interferences. Following optimization, three correct and accurate (<2%) isotope ratios were obtained with 77Se, 78Se, 80Se and 82Se. The optimized method was then applied to an arable and a forest soil submitted to an aging process (drying/wetting cycles) during three months, to which 77Se(IV) was previously added. The results showed that ambient Se was at steady state in terms of water leachability, partition between soil solid phases (exchangeable Se and Se associated to organic matter) and speciation. At the opposite, the retention strength, solid phase partition and speciation of 77Se(IV) were modified during the experiment time-course and presented different kinetics. 77Se(IV) behavior tended to be similar to the one of ambient Se but still remained less strongly retained and chemically transformed at three months. We concluded that kinetically limited processes are involved in Se retention and transformation in soils and that commonly used short-term experiments (<1 month) do not consider them properly. Otherwise, it seems more judicious to study ambient Se to infer the processes and parameters used in long-term risk assessment modeling. Since three correct and accurate Se isotope ratios were obtained, this new methodology can be further used to simultaneous monitor the reactivity of three different Se forms (e.g., added Se(IV), Se(VI) or Se(0), ambient Se), that will be useful for both soil Se contamination and supplementation contexts.

The Combination of DGT Technique and Traditional Chemical Methods for Evaluation of Cadmium Bioavailability in Contaminated Soils with Organic Amendment

PubMed Central

Yao, Yu; Sun, Qin; Wang, Chao; Wang, Pei-Fang; Miao, Ling-Zhan; Ding, Shi-Ming

2016-01-01

Organic amendments have been proposed as a means of remediation for Cd-contaminated soils. However, understanding the inhibitory effects of organic materials on metal immobilization requires further research. In this study colza cake, a typical organic amendment material, was investigated in order to elucidate the ability of this material to reduce toxicity of Cd-contaminated soil. Available concentrations of Cd in soils were measured using an in situ diffusive gradients in thin films (DGT) technique in combination with traditional chemical methods, such as HOAc (aqua regia), EDTA (ethylene diamine tetraacetic acid), NaOAc (sodium acetate), CaCl2, and labile Cd in pore water. These results were applied to predict the Cd bioavailability after the addition of colza cake to Cd-contaminated soil. Two commonly grown cash crops, wheat and maize, were selected for Cd accumulation studies, and were found to be sensitive to Cd bioavailability. Results showed that the addition of colza cake may inhibit the growth of wheat and maize. Furthermore, the addition of increasing colza cake doses led to decreasing shoot and root biomass accumulation. However, increasing colza cake doses did lead to the reduction of Cd accumulation in plant tissues, as indicated by the decreasing Cd concentrations in shoots and roots. The labile concentration of Cd obtained by DGT measurements and the traditional chemical extraction methods, showed the clear decrease of Cd with the addition of increasing colza cake doses. All indicators showed significant positive correlations (p < 0.01) with the accumulation of Cd in plant tissues, however, all of the methods could not reflect plant growth status. Additionally, the capability of Cd to change from solid phase to become available in a soil solution decreased with increasing colza cake doses. This was reflected by the decreases in the ratio (R) value of CDGT to Csol. Our study suggests that the sharp decrease in R values could not only reflect the extremely low capability of labile Cd to be released from its solid phase, but may also be applied to evaluate the abnormal growth of the plants. PMID:27314376

The Combination of DGT Technique and Traditional Chemical Methods for Evaluation of Cadmium Bioavailability in Contaminated Soils with Organic Amendment.

PubMed

Yao, Yu; Sun, Qin; Wang, Chao; Wang, Pei-Fang; Miao, Ling-Zhan; Ding, Shi-Ming

2016-06-15

Organic amendments have been proposed as a means of remediation for Cd-contaminated soils. However, understanding the inhibitory effects of organic materials on metal immobilization requires further research. In this study colza cake, a typical organic amendment material, was investigated in order to elucidate the ability of this material to reduce toxicity of Cd-contaminated soil. Available concentrations of Cd in soils were measured using an in situ diffusive gradients in thin films (DGT) technique in combination with traditional chemical methods, such as HOAc (aqua regia), EDTA (ethylene diamine tetraacetic acid), NaOAc (sodium acetate), CaCl₂, and labile Cd in pore water. These results were applied to predict the Cd bioavailability after the addition of colza cake to Cd-contaminated soil. Two commonly grown cash crops, wheat and maize, were selected for Cd accumulation studies, and were found to be sensitive to Cd bioavailability. Results showed that the addition of colza cake may inhibit the growth of wheat and maize. Furthermore, the addition of increasing colza cake doses led to decreasing shoot and root biomass accumulation. However, increasing colza cake doses did lead to the reduction of Cd accumulation in plant tissues, as indicated by the decreasing Cd concentrations in shoots and roots. The labile concentration of Cd obtained by DGT measurements and the traditional chemical extraction methods, showed the clear decrease of Cd with the addition of increasing colza cake doses. All indicators showed significant positive correlations (p < 0.01) with the accumulation of Cd in plant tissues, however, all of the methods could not reflect plant growth status. Additionally, the capability of Cd to change from solid phase to become available in a soil solution decreased with increasing colza cake doses. This was reflected by the decreases in the ratio (R) value of CDGT to Csol. Our study suggests that the sharp decrease in R values could not only reflect the extremely low capability of labile Cd to be released from its solid phase, but may also be applied to evaluate the abnormal growth of the plants.

Development of an ultra-high-pressure liquid chromatography-tandem mass spectrometry multi-residue sulfonamide method and its application to water, manure slurry, and soils from swine rearing facilities.

PubMed

Shelver, Weilin L; Hakk, Heldur; Larsen, Gerald L; DeSutter, Thomas M; Casey, Francis X M

2010-02-19

An analytical method was developed using ultra-high-pressure liquid chromatography-triple quadrupole-tandem mass spectrometry (UHPLC-TQ-MS/MS) to simultaneously analyze 14 sulfonamides (SA) in 6 min. Despite the rapidity of the assay the system was properly re-equilibrated in this time. No carryover was observed even after high analyte concentrations. The instrumental detection limit based on signal-to-noise ratio (S/N)>3, was below 1 pg/microL (5 pg on column) for all SAs except sulfachloropyridazine. Surface water, ground water, soil, and slurry manure contained in storage ponds in and around swine [Sus scrofa domesticus] rearing facilities were analyzed. Sample cleanup for ground water and surface water included using solid phase extraction (SPE) using Oasis hydrophilic-lipophilic balance (HLB) cartridges. The soil and slurry manure required tandem strong anion exchange (SAX) and HLB solid phase extraction cartridges for sample cleanup. With few exceptions, the recoveries ranged from 60 to 100% for all matrices. The minimum detectable levels were below 2.0 ng/L for water, 30 ng/L for slurry manure, and 45 ng/kg for soil except for sulfachloropyridazine. The coefficient of variation (CV) was within 20% for most of the compounds analyzed. Using this method, sulfamethazine concentrations of 2250-5060 ng/L, sulfamethoxazole concentrations of 108-1.47 x 10(6)ng/L, and sulfathiazole concentrations of 785-1700 ng/L were found in the slurry manure. Sulfadimethoxine (2.0-32 ng/L), sulfamethazine (2.0-5.1 ng/L), and sulfamethoxazole (20.5-43.0 ng/L) were found in surface water and ground water. In top soil (0-15 cm), sulfamethazine ranged 34.5-663 ng/kg dry weight in those locations that received slurry manure as a nutrient; no SAs were found in the soil depths between 46 and 61 cm. The speed makes the method practical for medium to high throughput applications. The sensitivity and positive analyte identification make the method suitable for the demanding requirements for real world applications. Published by Elsevier B.V.

The fate of silver nanoparticles in soil solution--Sorption of solutes and aggregation.

PubMed

Klitzke, Sondra; Metreveli, George; Peters, Andre; Schaumann, Gabriele E; Lang, Friederike

2015-12-01

Nanoparticles enter soils through various pathways. In the soil, they undergo various interactions with the solution and the solid phase. We tested the following hypotheses using batch experiments: i) the colloidal stability of Ag NP increases through sorption of soil-borne dissolved organic matter (DOM) and thus inhibits aggregation; ii) the presence of DOM suppresses Ag oxidation; iii) the surface charge of Ag NP governs sorption onto soil particles. Citrate-stabilized and bare Ag NPs were equilibrated with (colloid-free) soil solution extracted from a floodplain soil for 24h. Nanoparticles were removed through centrifugation. Concentrations of free Ag ions and DOC, the specific UV absorbance at a wavelength of 254 nm, and the absorption ratio α254/α410 were determined in the supernatant. Nanoparticle aggregation was studied using time-resolved dynamic light scattering (DLS) measurement following the addition of soil solution and 1.5mM Ca(2+) solution. To study the effect of surface charge on the adsorption of Ag NP onto soil particles, bare and citrate-stabilized Ag NP, differing in the zeta potential, were equilibrated with silt at a solid-to-solution ratio of 1:10 and an initial Ag concentration range of 30 to 320 μg/L. Results showed that bare Ag NPs sorb organic matter, with short-chained organic matter being preferentially adsorbed over long-chained, aromatic organic matter. Stabilizing effects of organic matter only come into play at higher Ag NP concentrations. Soil solution inhibits the release of Ag(+) ions, presumably due to organic matter coatings. Sorption to silt particles was very similar for the two particle types, suggesting that the surface charge does not control Ag NP sorption. Besides, sorption was much lower than in comparable studies with sand and glass surfaces. Copyright © 2014. Published by Elsevier B.V.

Lability of Cd, Cu, and Zn in polluted soils treated with lime, beringite, and red mud and identification of a non-labile colloidal fraction of metals using istopic techniques.

PubMed

Lombi, Enzo; Hamon, Rebecca E; McGrath, Steve P; McLaughlin, Mike J

2003-03-01

The use of soil amendments has been proposed as a low input alternative for the remediation of metal polluted soils. However, little information is available concerning the stability, and therefore the longevity, of the remediation treatments when important soil parameters change. In this paper we investigate the effect of pH changes on the lability of heavy metals in soils treated with lime, beringite, and red mud using a modified isotopic dilution technique in combination with a stepwise acidification procedure. Significant amounts of nonlabile (fixed) Cu and Zn were found to be associated with colloids <0.2 microm in the solution phase. The results obtained indicated that the mobility of fixed colloidal metals is significant and increases with soil pH. This must be considered because most of the soil amendments are alkaline and increase soil pH. All the soil amendments significantly decreased the lability of Cd, Zn, and Cu in the soils as a whole. However, when the soils were re-acidified, the labile pool of metals increased sharply and in the case of lime and beringite, the lability of the metals was similar, at equal pH, to the untreated soil. In contrast the lability of metals in the red mud treated soils was always smaller than that in the untreated soils across the range of pH values tested. These results suggest that the mechanism of action of lime and beringite is similar and probably related to increased metal adsorption and precipitation of metal hydroxides and carbonates at high pH. In the case of red mud, a combination of pH dependent and independent mechanisms (possibly solid-phase diffusion or migration into micropores) may be responsible for the metal fixation observed.

Arsenic solid-phase speciation and reversible binding in long-term contaminated soils.

PubMed

Rahman, M S; Clark, M W; Yee, L H; Comarmond, M J; Payne, T E; Kappen, P; Mokhber-Shahin, L

2017-02-01

Historic arsenic contamination of soils occurs throughout the world from mining, industrial and agricultural activities. In Australia, the control of cattle ticks using arsenicals from the late 19th to mid 20th century has led to some 1600 contaminated sites in northern New South Wales. The effect of aging in As-mobility in two dip-site soil types, ferralitic and sandy soils, are investigated utilizing isotopic exchange techniques, and synchrotron X-ray adsorption spectroscopy (XAS). Findings show that historic soil arsenic is highly bound to the soils with >90% irreversibly bound. However, freshly added As (either added to historically loaded soils or pristine soils) has a significantly higher degree of As-accessibility. XAS data indicates that historic soil arsenic is dominated as Ca- (svenekite, & weilite), Al-(mansfieldite), and Fe- (scorodite) like mineral precipitates, whereas freshly added As is dominated by mineral adsorption surfaces, particularly the iron oxy-hydroxides (goethite and hematite), but also gibbsite and kaolin surfaces. SEM data further confirmed the presence of scorodite and mansfieldite formation in the historic contaminated soils. These data suggest that aging of historic soil-As has allowed neoformational mineral recrystallisation from surface sorption processes, which greatly reduces As-mobility and accessibility. Copyright © 2016 Elsevier Ltd. All rights reserved.

Occurrence of pesticide non extractable residues in physical and chemical fractions from two natural soils.

NASA Astrophysics Data System (ADS)

Andreou, K.; Jones, K.; Semple, K.

2009-04-01

Distribution of pesticide non extractable residues resulted from the incubation of two natural soils with each of the isoproturon, diazinon and cypermethrin pesticide was assessed in this study. Pesticide non extractable residues distribution in soil physical and chemical fractions is known to ultimately affect their fate. This study aimed to address the fate and behaviour of the non extractable residues in the context of their association with soil physical and chemical fractions with varying properties and characteristics. Non extractable residues were formed from incubation of each pesticide in the two natural soils over a period of 24 months. Soils containing the non extractable residues were fractionated into three solid phase fractions using a physical fractionation procedure as follows: Sediment (SED, >20 μm), (II) Microaggregate (MA, 20-2 μm) and (III) Colloid phase (COL, 2-0.05 μm). Each soil fraction was then fractionated into organic carbon chemical fractionations as follows: Fulvic acid (FA), Humic acid (HA) and Humin (HM). Significant amount of the pesticides was lost during the incubation period. Enrichment factors for the organic carbon and the 14C-pesticide residues were higher in the MA and COL fraction rather than the SED fraction. Greater association and enrichment of the fulvic acid fraction of the organic carbon in the soil was observed. Non extractable residues at the FA fraction showed to diminish while in the HA fraction were increased with decreasing the fraction size. An appreciable amount of non extractable residues were located in the HM fraction but this was less than the amount recovered in the humic substances. Long term fate of pesticide non extractable residues in the soil structural components is important in order to assess any risk associated with them.

Enzyme Sorption onto Soil and Biocarbon Amendments Alters Catalytic Capacity and Depends on the Specific Protein and pH

NASA Astrophysics Data System (ADS)

Foster, E.; Fogle, E. J.; Cotrufo, M. F.

2017-12-01

Enzymes catalyze biogeochemical reactions in soils and play a key role in nutrient cycling in agricultural systems. Often, to increase soil nutrients, agricultural managers add organic amendments and have recently experimented with charcoal-like biocarbon products. These amendments can enhance soil water and nutrient holding capacity through increasing porosity. However, the large surface area of the biocarbon has the potential to sorb nutrients and other organic molecules. Does the biocarbon decrease nutrient cycling through sorption of enzymes? In a laboratory setting, we compared the interaction of two purified enzymes β-glucosidase and acid phosphatase with a sandy clay loam and two biocarbons. We quantified the sorbed enzymes at three different pHs using a Bradford protein assay and then measured the activity of the sorbed enzyme via high-throughput fluorometric analysis. Both sorption and activity depended upon the solid phase, pH, and specific enzyme. Overall the high surface area biocarbon impacted the catalytic capacity of the enzymes more than the loam soil, which may have implications for soil nutrient management with these organic amendments.

Predicting sorption of pharmaceuticals and personal care products onto soil and digested sludge using artificial neural networks.

PubMed

Barron, Leon; Havel, Josef; Purcell, Martha; Szpak, Michal; Kelleher, Brian; Paull, Brett

2009-04-01

A comprehensive analytical investigation of the sorption behaviour of a large selection of over-the-counter, prescribed pharmaceuticals and illicit drugs to agricultural soils and freeze-dried digested sludges is presented. Batch sorption experiments were carried out to identify which compounds could potentially concentrate in soils as a result of biosolid enrichment. Analysis of aqueous samples was carried out directly using liquid chromatography-tandem mass spectrometry (LC-MS/MS). For solids analysis, combined pressurised liquid extraction and solid phase extraction methods were used prior to LC-MS/MS. Solid-water distribution coefficients (K(d)) were calculated based on slopes of sorption isotherms over a defined concentration range. Molecular descriptors such as log P, pK(a), molar refractivity, aromatic ratio, hydrophilic factor and topological surface area were collected for all solutes and, along with generated K(d) data, were incorporated as a training set within a developed artificial neural network to predict K(d) for all solutes within both sample types. Therefore, this work represents a novel approach using combined and cross-validated analytical and computational techniques to confidently study sorption modes within the environment. The logarithm plots of predicted versus experimentally determined K(d) are presented which showed excellent correlation (R(2) > 0.88), highlighting that artificial neural networks could be used as a predictive tool for this application. To evaluate the developed model, it was used to predict K(d) for meclofenamic acid, mefenamic acid, ibuprofen and furosemide and subsequently compared to experimentally determined values in soil. Ratios of experimental/predicted K(d) values were found to be 1.00, 1.00, 1.75 and 1.65, respectively.

Electrokinetic removal of radionuclides contained in scintillation liquids absorbed in soil type Phaeozem.

PubMed

Valdovinos, V; Monroy-Guzmán, F; Bustos, E

2016-10-01

Control samples of scintillation liquids - Phaeozem soil mixtures were prepared with different scintillation liquids as the support electrolyte, Install Gel ® XF, (Ultima Gold AB™ and Ultima Gold XR™), to construct the polarization curves, and to select the cell potential with the highest mass transfer to remove 24 Na (15 h) and 99m Tc (6 h) as radiotracers from polluted Phaeozem soil. During the electrokinetic treatment (EKT), the removal of radionuclides contained in scintillation liquids absorbed in Phaeozem soil, liquid phase was characterized by Gas Chromatography coupled with a Flame Ionization Detector (GC-FID) and Fourier Transform Infrared Spectrometry (FTIR), solids by FTIR, before and after the application of cell potential. In this sense, the support electrolyte was selected based on the highest current generated (1 mA), as in the case of scintillation liquid 50% Ultima Gold XR™ + 50% Water (1:1), which was used for 6 h in the presence of a mesh and a titanium rod, as anode and cathode, respectively. Finally, the removal percentage accumulated in the liquid phase after the EKT of Phaeozem soil polluted by 99m Tc was 61% close to the anode after 4 h. It was also 61% for 24 Na close to cathode after 2 h, and after 4 h it was 71.8%. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling Fate and Transport of Rotavirus in Surface Flow by Integrating WEPP and a Pathogen Transport Model

NASA Astrophysics Data System (ADS)

Bhattarai, R.; Kalita, P. K.; Davidson, P. C.; Kuhlenschmidt, M. S.

2012-12-01

More than 3.5 million people die each year from a water related diseases in this world. Every 20 seconds, a child dies from a water-related illness. Even in a developed country like the United States, there have been at least 1870 outbreaks associated with drinking water during the period of 1920 to 2002, causing 883,806 illnesses. Most of these outbreaks are resulted due to the presence of microbial pathogens in drinking water. Rotavirus infection has been recognized as the most common cause of diarrhea in young children throughout the world. Laboratory experiments conducted at the University of Illinois have demonstrated that recovery of rotavirus has been significantly affected by climatic and soil-surface conditions like slope, soil types, and ground cover. The objective of this study is to simulate the fate and transport of Rotavirus in overland and near-surface flow using a process-based model. In order to capture the dynamics of sediment-bound pathogens, the Water Erosion Prediction Project (WEPP) is coupled with the pathogen transport model. Transport of pathogens in overland flow can be simulated mathematically by including terms for the concentration of the pathogens in the liquid phase (in suspension or free-floating) and the solid phase (adsorbed to the fine solid particles like clay and silt). Advection, adsorption, and decay processes are considered. The mass balance equations are solved using numerical technique to predict spatial and temporal changes in pathogen concentrations in two phases. Outputs from WEPP simulations (flow velocity, depth, saturated conductivity and the soil particle fraction exiting in flow) are transferred as input for the pathogen transport model. Three soil types and three different surface cover conditions have been used in the experimental investigations. Results from these conditions have been used in calibrating and validating the simulation results. Bare surface conditions have produced very good agreement between observed and predicted results; however, transport of pathogens from vegetated surface has been challenging. This paper will provide concepts of the pathogen transport model, integration with WEPP, and results obtained from the modeling framework.

Analytical Determination of KDOC-Values of Polycyclic Musk Compounds with HS-SPME and GC/MS/MS

NASA Astrophysics Data System (ADS)

Böhm, L.; Düring, R.-A.

2009-04-01

Polycyclic musk compounds, used as fragrances in cosmetics and detergents, get into rivers via domestic wastewater and sewage treatment plants and with sewage sludge as fertilizer into soils. Because of their persistence and lipophilic character they accumulate in biota, so they are pollutants with environmental relevance. The coefficient KDOC is used to quantify the distribution of substances between aqueous phase and dissolved organic matter (DOM) which is quantified by the determination of dissolved organic carbon (DOC). DOM is of specific relevance for the transport and fate of persistent and lipophilic compounds in the environment. The affinity to DOM increases, the more lipophilic a substance is. So the environmental mobility is enhanced with increasing binding on DOM. For that reason, measured KDOC-values are important to predict the fate and behaviour of chemicals in the environment and should be used for environmental fate modelling purposes. LITZ ET AL. (2007) state that, to carry out a risk-assessment for polycyclic musk compounds, further research on their sorption-behaviour is necessary. For the determination of KDOC-values, different concentrations of humic acid were spiked with a multi-component stock solution. The samples were analysed with headspace solid-phase microextraction in combination with gas chromatography coupled with mass spectrometry (HS-SPME GC/MS/MS). The KDOC-values were calculated according to YABUTA ET AL. (2004). The method was validated with single substance stock solutions and with polycyclic aromatic hydrocarbons (PAHs). The results show that the method is applicable, repeatable and suitable to get KDOC-values for many substances very fast, cheap and solvent-free. With our results KDOC-values for polycyclic musk compounds were determined for the first time. Literature LITZ, N. TH., MüLLER, J. AND BöHMER, W. (2007): Occurrence of Polycyclic Musks in Sewage Sludge and their Behaviour in Soils and Plants. Part 2: Investigation of Polycyclic Musks in Soils and Plants. J Soils Sediments 7: 36-44 YABUTA, H., FUKUSHIMA, M., TANAKA, F., ICHIKAWA, H. AND TATSUMI, K. (2004): Solid-phase Microextraction for the Evaluation of Partition Coefficients of a Chlorinated Dioxin and Hexachlorobenzene into Humic Substances. Anal. Sci. 20: 787-791

High-performance liquid chromatography (HPLC) as a tool for monitoring the fate of fluazinam in soil.

PubMed

Hakala, Kati P; Tuomainen, Päivi M; Yli-Halla, Markku J; Hartikainen, Helinä

2014-01-01

Fluazinam is a widely used pesticide employed against the fungal disease late blight in potato cultivation. A specific, repeatable, and rapid high-performance liquid chromatography (HPLC) method utilizing a diode array detector (DAD) was developed to determine the presence of fluazinam in soil. The method consists of acetonitrile (ACN) extraction, clean-up with solid-phase extraction (SPE), and separation using a mobile phase consisting of 70% ACN and 30% water (v/v), including 0.02% acetic acid. HPLC was performed with a C18 column and the detection wavelength was 240 nm. The method was successfully applied to an incubation experiment and to soil samples taken from potato fields where fluazinam had been applied two to three times during the on-going growing season. In the 90-day incubation experiment, analytical standard fluazinam and the commercial fungicide Shirlan(®) were added to soil samples that had never been treated with fluazinam, and were then extracted with ACN and 0.01 M calcium chloride (CaCl2). Fluazinam was not extractable with CaCl2, indicating that it does not leach to watercourses in the dissolved form. Recovery with ACN extraction for sandy soils was 72-95% immediately after application and 53-73% after 90 days of incubation. Out of the eight potato field soil samples, fluazinam was found in two samples at concentrations of 2.1 mg kg(-1) and 1.9 mg kg(-1), well above the limit of quantification (0.1 mg kg(-1)).

Sorption of Fluorotelomer Sulfonates, Fluorotelomer Sulfonamido Betaines, and a Fluorotelomer Sulfonamido Amine in National Foam Aqueous Film-Forming Foam to Soil.

PubMed

Barzen-Hanson, Krista A; Davis, Shannon E; Kleber, Markus; Field, Jennifer A

2017-11-07

During fire-fighter training, equipment testing, and emergency responses with aqueous film-forming foams (AFFFs), milligrams per liter concentrations of anionic, zwitterionic, and cationic per- and polyfluoroalkyl substances (PFASs) enter the environment. Because the behavior of zwitterionic and cationic PFASs in the subsurface is unknown, batch sorption experiments were conducted using National Foam AFFF, which contains anionic fluorotelomer sulfonates (FtSs), zwitterionic fluorotelomer sulfonamido betaines (FtSaBs), and cationic 6:2 fluorotelomer sulfonamido amine (FtSaAm). Sorption of the FtSs, FtSaBs, and 6:2 FtSaAm to six soils with varying organic carbon, effective cation-exchange capacity, and anion-exchange capacity was evaluated to determine sorption mechanisms. Due to the poor recovery of the FtSaBs and 6:2 FtSaAm with published PFAS soil extraction methods, a new soil extraction method was developed to achieve good (90-100%) recoveries. The 6:2 FtSaAm was depleted from the aqueous phase in all but one soil, which is attributed to electrostatic and hydrophobic interactions. Sorption of the FtSs was driven by hydrophobic interactions, while the FtSaBs behave more like cations that strongly associate with the solid phase relative to groundwater. Thus, the sorption mechanisms of the FtSs, FtSaBs, and 6:2 FtSaAm are more complex than expected and cannot be predicted by bulk soil properties.

Physicochemical characterization of coke-plant soil for the assessment of polycyclic aromatic hydrocarbon availability and the feasibility of phytoremediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahn, S.; Werner, D.; Luthy, R.G.

Coke oven site soil was characterized to assess the particle association and availability of polycyclic aromatic hydrocarbons (PAHs). We identified various carbonaceous materials including coal, coke, pitch, and tar decanter sludge. Most of the PAHs were associated with the polymeric matrix of tar sludge or hard pitch as discrete particles, coatings on soil mineral particles, or complex aggregates. The PAH availability from these particles was very low due to hindered diffusive release from solid tar or pitch with apparent diffusivities of 6 x 10{sup -15} for phenanthrene, 3 x 10{sup -15} for pyrene, and 1 x 10{sup -15} cm{sup 2}/smore » for benzo(a)pyrene. Significant concentrations of PAHs were observed in the interior of solid tar aggregates with up to 40,000 mg/kg total PAHs. The release of PAHs from the interior of such particles requires diffusion over a substantial distance, and semipermeable membrane device tests confirmed a very limited availability of PAHs. These findings explain the results from three years of phytoremediation of the site soil, for which no significant changes in the total PAH concentrations were observed in the test plot samples. The observed low bioavailability of PAHs probably inhibited PAH phytoremediation, as diffusion-limited mass transfer would limit the release of PAHs to the aqueous phase.« less

Solid phase microextraction-high performance liquid chromatographic determination of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in the presence of sodium dodecyl sulfate surfactant.

PubMed

Malik, Ashok Kumar; Rai, Parmod Kumar

2008-07-01

A simple and sensitive method has been developed using preconcentration technique solid phase microextraction (SPME) and analytical technique HPLC-UV for the determination of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from the environmental samples. Aqueous solution of anionic surfactant SDS was used for the extraction of both nitramine high explosives, viz., HMX and RDX from soil samples which were subsequently sorbed on SPME fiber. The static desorption was carried out in the desorption chamber of the SPME-HPLC interface in the presence of mobile phase ACN/methanol/water (30:35:35) and the subsequent chromatographic analysis at a flow rate of 0.5 mL/min and detection at 230 nm. For this purpose, a C(18), 5 microm RP analytical column was used as a separation medium in this method. Several parameters relating to SPME, e.g., adsorption/desorption time, concentration of salt, stirring rate, etc., were optimized. The method was linear over the range of 20-400 ng/mL for HMX and RDX standards in the presence of surfactant in aqueous phase, respectively. The correlation coefficient (R(2)) for HMX and RDX are 0.9998 and 0.9982, respectively. With SPME, the detection limits (S/N = 3) in ng/mL are 0.05 and 0.1 for HMX and RDX, respectively in the presence of the SDS surfactant. The developed method has been applied successfully to the analysis of real environmental samples like bore well water, river water, and ground alluvial soil.

Organic Acids Regulation of Chemical-Microbial Phosphorus Transformations in Soils.

PubMed

Menezes-Blackburn, Daniel; Paredes, Cecilia; Zhang, Hao; Giles, Courtney D; Darch, Tegan; Stutter, Marc; George, Timothy S; Shand, Charles; Lumsdon, David; Cooper, Patricia; Wendler, Renate; Brown, Lawrie; Blackwell, Martin; Wearing, Catherine; Haygarth, Philip M

2016-11-01

We have used an integrated approach to study the mobility of inorganic phosphorus (P) from soil solid phase as well as the microbial biomass P and respiration at increasing doses of citric and oxalic acid in two different soils with contrasting agronomic P status. Citric or oxalic acids significantly increased soil solution P concentrations for doses over 2 mmol kg -1 . However, low organic acid doses (<2 mmol kg -1 ) were associated with a steep increase in microbial biomass P, which was not seen for higher doses. In both soils, treatment with the tribasic citric acid led to a greater increase in soil solution P than the dibasic oxalic acid, likely due to the rapid degrading of oxalic acids in soils. After equilibration of soils with citric or oxalic acids, the adsorbed-to-solution distribution coefficient (K d ) and desorption rate constants (k -1 ) decreased whereas an increase in the response time of solution P equilibration (T c ) was observed. The extent of this effect was shown to be both soil and organic acid specific. Our results illustrate the critical thresholds of organic acid concentration necessary to mobilize sorbed and precipitated P, bringing new insight on how the exudation of organic acids regulate chemical-microbial soil phosphorus transformations.

Installation Restoration Program. Phase 2. Confirmation/Quantification. Stage 1 for Minot Air Force Base, Minot, North Dakota. Volume 3. Appendices G through M

DTIC Science & Technology

1988-10-01

TOTAL DISSOVLED SOLIDS 3523/017 1896 1918 --- 3538/024 2625 2567 --- IV. PETROLEUM HYDROCARBON DUPLICATE ANALYSIS WAS NOT DONE DUE TO INSUFFICIENT...Characterized existing hydrogeologic conditions, prepared hydrologic budgets, delineated productive aquifers, performed safe yield determinations , and...New Jersey to determine suitability for building construction. * Supervised soil borings program at large waste disposal facility in Model City, New

Chemical structure of soil organic matter in slickspots as investigated by advanced solid-state NMR

USDA-ARS?s Scientific Manuscript database

Slickspot soils are saline, and knowledge of their humic chemistry would contribute to our limited understanding how salinity affects soil C and N stocks. We characterized humic acids (HAs) from slickspot soils with solid-state 13C nuclear magnetic resonance (NMR). Expanding on previous use of cross...

Corrosion of bare carbon steel as a passive sensor to assess moisture availability for biological activity in Atacama Desert soils.

PubMed

Cáceres, Luis; Davila, Alfonso F; Soliz, Alvaro; Saldivia, Jessica

2018-02-28

Here we consider that the corrosion of polished bared metal coupons can be used as a passive sensor to detect or identify the lower limit of water availability suitable for biological activity in Atacama Desert soils or solid substrates. For this purpose, carbon steel coupons were deposited at selected sites along a west-east transect and removed at predetermined times for morphological inspection. The advantage of this procedure is that the attributes of the oxide layer (corrosion extent, morphology and oxide phases) can be considered as a fingerprint of the atmospheric moisture history at a given time interval. Two types of coupons were used, long rectangular shaped ones that were half-buried in a vertical position, and square shaped ones that were deposited on the soil surface. The morphological attributes observed by SEM inspection were found to correlate to the so-called humectation time which is determined from local meteorological parameters. The main finding was that the decreasing trend of atmospheric moisture along the transect was closely related to corrosion behaviour and water soil penetration. For instance, at the coastal site oxide phases formed on the coupon surface rapidly evolve into well-crystallized species, while at the driest inland site Lomas Bayas only amorphous oxide was observed on the coupons.

Corrosion of Bare Carbon Steel as a Passive Sensor to Assess Moisture Availability for Biological Activity in Atacama Desert Soils

NASA Technical Reports Server (NTRS)

Caceres, Luis; Davila, Alfonso F.; Soliz, Alvaro; Saldivia, Jessica

2018-01-01

In this work we suggest the corrosion of polished bared metal coupons as a passive sensor to detect or identify the lower limit of water availability that could be suitable for biological activity in the Atacama Desert on soil or solid substrates. For this purpose, carbon steel coupons were deposited in selected sites along a west-east transect and removed at predetermined times for morphological inspection. The advantage of this procedure is that the attributes of the oxide layer (corrosion extent, morphology and oxide phases) can be considered as a fingerprint of the atmospheric moisture history at a given time interval. Two types of coupons were used, a long rectangular shape that are half-buried in a vertical position, and square shape that are deposited on the soil surface. The morphological attributes observed by SEM inspection is correlated to the so-called humectation time which is determined from local meteorological parameters. The main result is that the decreasing trend of atmospheric moisture along the transect is closely related to corrosion behavior and water soil penetration. For instance, while in the coastal site oxide phases formed on the coupon surface rapidly evolve to well- crystallized species, in the driest inland site Lomas Bayas only amorphous oxide is observed.

Assessment of elemental mobility in soil using a fluidised bed approach with on-line ICP-MS analysis.

PubMed

Beeston, Michael Philip; Glass, Hylke Jan; van Elteren, Johannes Teun; Slejkovec, Zdenka

2007-09-19

A new method has been developed to analyse the mobility of elements within soils employing counter-current flow soil contacting in a fluidised bed (FB) column. This method alleviates the problem of irreproducible peaks suffered by state-of-the-art micro-column techniques as a result of particle compaction. Reproducible extraction profiles are produced through the leaching of soil with a linear gradient of 0.05 mol L(-1) ammonium sulphate to 0.11 mol L(-1) acetic acid using a high pressure liquid chromatography (HPLC) quaternary pump, and the continuous monitoring of the elements in the leachate with inductively coupled plasma mass spectrometry (ICP-MS). Quantification of the procedure is achieved with an external flow injection (FI) calibration method. Flow rate and FB column length were investigated as critical parameters to the efficiency of the extraction methodology. It was found that an increase in the column length from 10 to 20 cm using a flow rate of 0.15 mL min(-1) produced the same increase in extracted elemental concentration as an increase in flow rate from 0.15 to 0.30 mL min(-1). In both examples, the increase in the concentration of elements leached from the soil may be ascribed to the increase in the concentration gradient between the solid and liquid. The exhaustive nature of the technique defines the maximum leachable concentration within the operationally defined leaching parameters of the exchangeable phase, providing a more accurate assessment of the risk associated with the elements in the soil for the phase providing the greatest risk to the environment. The multi-elemental high sensitivity nature of the on-line detector provides an accurate determination of the associations present between the elements in the soil, and the identification of multiple phases within the exchangeable phase through the presence of multiple peaks in the extraction profiles. It is possible through the deconvolution of these extraction profiles that the concentration corresponding to the peaks identified can be defined.

Adsorption and Retardation of PFASs in Soil

NASA Astrophysics Data System (ADS)

Chen, W.; Yan, N.; Fu, X.; Carroll, K. C.; Holguin, F. O. O.; Brusseau, M. L.

2017-12-01

Per- and poly-fluorinated alkyl substances (PFASs) are emerging contaminants of concern that are present in the subsurface at numerous military and industrial facilities. Knowledge of the retention behavior of these compounds in the subsurface environment is critical for effective risk characterization and remediation. The objective of this research is to investigate the role of adsorption at the air-water interface on PFAS retention in vadose-zone systems. Surface tensions were measured for select PFAS to determine interfacial adsorption coefficients. Column experiments were conducted to characterize retardation and transport under saturated and unsaturated flow conditions. The impact of soil properties and groundwater constituents on surface tension, solid-phase adsorption, and interfacial adsorption was investigated.

Long-term batch study of sorption, transformation and extractability to characterize the fate of the veterinary antibiotic sulfadiazine

NASA Astrophysics Data System (ADS)

Sittig, Stephan; Kasteel, Roy; Groeneweg, Joost; Vereecken, Harry

2010-05-01

The occurrence of veterinary antibiotic substances in various environmental compartments is of growing concern. Once released into the environment (e.g. via manure), these organic substances can cause changes in the composition of microbial populations, provoke the development and spreading of resistance genes and finally reach the food chain. The substance under study is the veterinary antibiotic sulfadiazine (SDZ), which belongs to the chemical group of the sulfonamides. These compounds are widely applied in animal husbandry. There are hardly any studies on the macroscopic sorption and desorption behaviour in combination with transformation processes, particularly investigating the sorbed fraction. We are conducting long-term batch sorption experiments to characterize the partitioning between the liquid and the solid phases as well as formation of transformation products. A sequential extraction procedure enables us to analyse the composition of the various sorbed fractions. We applied 14C-labelled SDZ in aqueous solution to fresh soil, originating from an agricultural field (silty loam). Adsorption and desorption studies are conducted for the duration of 60 d and 80 d, respectively. Unique setups for single time-steps allow us to trace the development of the partition process between the liquid and the solid phase and also partitioning within the solid phase. The composition of these liquid phases concerning the parent substance and the transformation products is analyzed. Using Radio-HPLC we find at least five transformation products: 4-hydroxy-sulfadiazine (4-OH-SDZ), 4-(2-iminopyrimidin-1(2H)-yl)-aniline (An-SDZ) and additionally three yet unknown products. By means of a sequential extraction, differently strong bound fractions of the compound can be distinguished. Extractions consist of a mild method (0.01 M CaCl2-solution; 24 h) followed by a methanol extraction (4 h). Finally, a residual fraction is gained by microwave extraction at an elevated temperature (150°C) and pressure (mixture of water and acetonitril, 4:1). Bound residues are determined by combustion. The course of the kinetic adsorption/desorption processes as well as the partitioning of the compound over the various solid phase fractions is observed. Sorption is time-dependent and strongly non-linear. The topsoil shows a significantly higher sorption affinity than the subsoil. While the amount of radioactivity sorbed to the soil matrix increases with time, the extractability decreases significantly, i. e. at the end of the experimental time there is no yield with mild extraction methods. On the contrary, after 60 d, there is still a considerably mass gained with the microwave extraction. Desorption is very slow due to hysteresis. In the topsoil transformation occurs with higher rates, leading to more detectable transformation products as in the subsoil. With our experimental setup it will be possible to set up a kinetic modell for the partitioning of the solute between the liquid and the solid phase. This description will also include an estimation of the transformation parameters.

Percent recovery of low influent concentrations of microorganism surrogates in small sand columns

NASA Astrophysics Data System (ADS)

Stevenson, M. E.; Blaschke, A. P.

2012-04-01

In order to develop a dependable method to calculate the setback distance of a drinking water well from a potential point of microbiological contamination, surrogates are used to perform field tests to avoid using pathogenic micro-organisms. One such surrogate used to model the potential travel time of microbial contamination is synthetic microspheres. The goal of this study is to examine the effect of differing influent colloid concentrations on the percent recovery of microbial surrogates after passing through a soil column. Similar studies have been done to investigate blocking of ideal attachment sites using concentrations between 106 and 1010 particles ml-1. These high concentrations were necessary due to the detection limit of the measuring technique used; however, our measuring technique allows us to test input concentrations ranging from 101 to 106 particles ml-1. These low concentrations are more similar to the concentrations of pathogenic microorganisms present in nature. We have tested the enumeration of 0.5 μm microspheres using a solid-phase cytometer and evaluated their transport in small sand columns. Fluorescent microspheres were purchased for this study with carboxylated surfaces. The soil columns consist of Plexiglas tubes, 30 cm long and 7 cm in diameter, both filled with the same coarse sand. Bromide was used as a conservative tracer, to estimate pore-water velocity and dispersivity, and bromide concentrations were analysed using ion chromatography and bromide probes. Numerical modelling was done using CXTFIT and HYDRUS-1D software programs. The 0.5 μm beads were enumerated in different environmental waters using solid-phase cytometry and compared to counts in sterile water in order to confirm the accuracy of the method. The solid-phase cytometer was able to differentiate the 0.5 μm beads from naturally present autofluorescent particles and bacteria, and therefore, is an appropriate method to enumerate this surrogate.

Arsenic chemistry in soils and sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fendorf, S.; Nico, P.; Kocar, B.D.

2009-10-15

Arsenic is a naturally occurring trace element that poses a threat to human and ecosystem health, particularly when incorporated into food or water supplies. The greatest risk imposed by arsenic to human health results from contamination of drinking water, for which the World Health Organization recommends a maximum limit of 10 {micro}g L{sup -1}. Continued ingestion of drinking water having hazardous levels of arsenic can lead to arsenicosis and cancers of the bladder, skin, lungs and kidneys. Unfortunately, arsenic tainted drinking waters are a global threat and presently having a devastating impact on human health within Asia. Nearly 100 millionmore » people, for example, are presently consuming drinking water having arsenic concentrations exceeding the World Health Organization's recommended limit (Ahmed et al., 2006). Arsenic contamination of the environment often results from human activities such as mining or pesticide application, but recently natural sources of arsenic have demonstrated a devastating impact on water quality. Arsenic becomes problematic from a health perspective principally when it partitions into the aqueous rather than the solid phase. Dissolved concentrations, and the resulting mobility, of arsenic within soils and sediments are the combined result of biogeochemical processes linked to hydrologic factors. Processes favoring the partitioning of As into the aqueous phase, potentially leading to hazardous concentrations, vary extensively but can broadly be grouped into four categories: (1) ion displacement, (2) desorption (or limited sorption) at pH values > 8.5, (3) reduction of arsenate to arsenite, and (4) mineral dissolution, particularly reductive dissolution of Fe and Mn (hydr)oxides. Although various processes may liberate arsenic from solids, a transition from aerobic to anaerobic conditions, and commensurate arsenic and iron/manganese reduction, appears to be a dominant, but not exclusive, means by which high concentrations of dissolved arsenic are generated. Within the subsequent sections of this chapter, we explore and describe the biological and chemical processes that control the partitioning of arsenic between the solid and aqueous phase.« less

Analysis of perfluorinated carboxylic acids in soils II: optimization of chromatography and extraction.

PubMed

Washington, John W; Henderson, W Matthew; Ellington, J Jackson; Jenkins, Thomas M; Evans, John J

2008-02-15

With the objective of detecting and quantitating low concentrations of perfluorinated carboxylic acids (PFCAs), including perfluorooctanoic acid (PFOA), in soils, we compared the analytical suitability of liquid chromatography columns containing three different stationary phases, two different liquid chromatography-tandem mass spectrometry (LC/MS/MS) systems, and eight combinations of sample-extract pretreatments, extractions and cleanups on three test soils. For the columns and systems we tested, we achieved the greatest analytical sensitivity for PFCAs using a column with a C(18) stationary phase in a Waters LC/MS/MS. In this system we achieved an instrument detection limit for PFOA of 270 ag/microL, equating to about 14 fg of PFOA on-column. While an elementary acetonitrile/water extraction of soils recovers PFCAs effectively, natural soil organic matter also dissolved in the extracts commonly imparts significant noise that appears as broad, multi-nodal, asymmetric peaks that coelute with several PFCAs. The intensity and elution profile of this noise is highly variable among soils and it challenges detection of low concentrations of PFCAs by decreasing the signal-to-noise contrast. In an effort to decrease this background noise, we investigated several methods of pretreatment, extraction and cleanup, in a variety of combinations, that used alkaline and unbuffered water, acetonitrile, tetrabutylammonium hydrogen sulfate, methyl-tert-butyl ether, dispersed activated carbon and solid-phase extraction. For the combined objectives of complete recovery and minimization of background noise, we have chosen: (1) alkaline pretreatment; (2) extraction with acetonitrile/water; (3) evaporation to dryness; (4) reconstitution with tetrabutylammonium-hydrogen-sulfate ion-pairing solution; (5) ion-pair extraction to methyl-tert-butyl ether; (6) evaporation to dryness; (7) reconstitution with 60/40 acetonitrile/water (v/v); and (8) analysis by LC/MS/MS. Using this method, we detected in all three of our test soils, endogenous concentrations of all of our PFCA analytes, C(6) through C(10)-the lowest concentrations being roughly 30 pg/g of dry soil for perfluorinated hexanoic and decanoic acids in an agricultural soil.

Two-liquid-phase slurry bioreactors to enhance the degradation of high-molecular-weight polycyclic aromatic hydrocarbons in soil.

PubMed

Villemur, R; Déziel, E; Benachenhou, A; Marcoux, J; Gauthier, E; Lépine, F; Beaudet, R; Comeau, Y

2000-01-01

High-molecular-weight (HMW) polycyclic aromatic hydrocarbons (PAHs) are pollutants that persist in the environment due to their low solubility in water and their sequestration by soil and sediments. The addition of a water-immiscible, nonbiodegradable, and biocompatible liquid, silicone oil, to a soil slurry was studied to promote the desorption of PAHs from soil and to increase their bioavailability. First, the transfer into silicone oil of phenanthrene, pyrene, chrysene, and benzo[a]pyrene added to a sterilized soil (sandy soil with 0.65% total volatile solids) was measured for 4 days in three two-liquid-phase (TLP) slurry systems each containing 30% (w/v) soil but different volumes of silicone oil (2.5%, 7.5%, and 15% [v/v]). Except for chrysene, a high percentage of these PAHs was transferred from soil to silicone oil in the TLP slurry system containing 15% silicone oil. Rapid PAH transfer occurred during the first 8 h, probably resulting from the extraction of nonsolubilized and of poorly sorbed PAHs. This was followed by a period in which a slower but constant transfer occurred, suggesting extraction of more tightly bound PAHs. Second, a HMW PAH-degrading consortium was enriched in a TLP slurry system with a microbial population isolated from a creosote-contaminated soil. This consortium was then added to three other TLP slurry systems each containing 30% (w/v) sterilized soil that had been artificially contaminated with pyrene, chrysene, and benzo[a]pyrene, but different volumes of silicone oil (10%, 20%, and 30% [v/v]). The resulting TLP slurry bioreactors were much more efficient than the control slurry bioreactor containing the same contaminated soil but no oil phase. In the TLP slurry bioreactor containing 30% silicone oil, the rate of pyrene degradation was 19 mg L(-)(1) day(-)(1) and no pyrene was detected after 4 days. The degradation rates of chrysene and benzo[a]pyrene in the 30% TLP slurry bioreactor were, respectively, 3.5 and 0.94 mg L(-)(1) day(-)(1). Low degradation of pyrene and no significant degradation of chrysene and benzo[a]pyrene occurred in the slurry bioreactor. This is the first report in which a TLP system was combined with a slurry system to improve the biodegradation of PAHs in soil.

Airborne soil organic particles generated by precipitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Bingbing; Harder, Tristan H.; Kelly, Stephen T.

Airborne organic particles play a critical role in Earth’s climate 1, public health 2, air quality 3, and hydrological and carbon cycles 4. However, sources and formation mechanisms for semi-solid and solid organic particles 5 are poorly understood and typically neglected in atmospheric models 6. Laboratory evidence suggests that fine particles can be formed from impaction of mineral surfaces by droplets 7. Here, we use chemical imaging of particles collected following rain events in the Southern Great Plains, Oklahoma, USA and after experimental irrigation to show that raindrop impaction of soils generates solid organic particles. We find that after rainmore » events, sub-micrometre solid particles, with a chemical composition consistent with soil organic matter, contributed up to 60% of atmospheric particles. Our irrigation experiments indicate that intensive water impaction is sufficient to cause ejection of airborne soil organic particles from the soil surface. Chemical imaging and micro-spectroscopy analysis of particle physico-chemical properties suggest that these particles may have important impacts on cloud formation and efficiently absorb solar radiation. Lastly, we suggest that raindrop-induced formation of solid organic particles from soils may be a widespread phenomenon in ecosystems such as agricultural systems and grasslands where soils are exposed to strong, episodic precipitation events 8.« less

Airborne soil organic particles generated by precipitation

DOE PAGES

Wang, Bingbing; Harder, Tristan H.; Kelly, Stephen T.; ...

2016-05-02

Airborne organic particles play a critical role in Earth’s climate 1, public health 2, air quality 3, and hydrological and carbon cycles 4. However, sources and formation mechanisms for semi-solid and solid organic particles 5 are poorly understood and typically neglected in atmospheric models 6. Laboratory evidence suggests that fine particles can be formed from impaction of mineral surfaces by droplets 7. Here, we use chemical imaging of particles collected following rain events in the Southern Great Plains, Oklahoma, USA and after experimental irrigation to show that raindrop impaction of soils generates solid organic particles. We find that after rainmore » events, sub-micrometre solid particles, with a chemical composition consistent with soil organic matter, contributed up to 60% of atmospheric particles. Our irrigation experiments indicate that intensive water impaction is sufficient to cause ejection of airborne soil organic particles from the soil surface. Chemical imaging and micro-spectroscopy analysis of particle physico-chemical properties suggest that these particles may have important impacts on cloud formation and efficiently absorb solar radiation. Lastly, we suggest that raindrop-induced formation of solid organic particles from soils may be a widespread phenomenon in ecosystems such as agricultural systems and grasslands where soils are exposed to strong, episodic precipitation events 8.« less

Arsenic accumulation in irrigated agricultural soils in Northern Greece.

PubMed

Casentini, B; Hug, S J; Nikolaidis, N P

2011-10-15

The accumulation of arsenic in soils and food crops due to the use of arsenic contaminated groundwater for irrigation has created worldwide concern. In the Chalkidiki prefecture in Northern Greece, groundwater As reach levels above 1000μg/L within the Nea Triglia geothermal area. While this groundwater is no longer used for drinking, it represents the sole source for irrigation. This paper provides a first assessment of the spatial extent of As accumulation and of As mobility during rainfall and irrigation periods. Arsenic content in sampled soils ranged from 20 to 513mg/kg inside to 5-66mg/kg outside the geothermal area. Around irrigation sprinklers, high As concentrations extended horizontally to distances of at least 1.5m, and to 50cm in depth. During simulated rain events in soil columns (pH=5, 0μg As/L), accumulated As was quite mobile, resulting in porewater As concentrations of 500-1500μg/L and exposing plant roots to high As(V) concentrations. In experiments with irrigation water (pH=7.5, 1500μg As/L), As was strongly retained (50.5-99.5%) by the majority of the soils. Uncontaminated soils (<30mg As/kg) kept soil porewater As concentrations to below 50μg/L. An estimated retardation factor R(f)=434 for weakly contaminated soil (<100mg/kg) indicates good ability to reduce As mobility. Highly contaminated soils (>500mg/kg) could not retain any of the added As. Invoked mechanisms affecting As mobility in those soils were adsorption on solid phases such as Fe/Mn-phases and As co-precipitation with Ca. Low As accumulation was found in collected olives (0.3-25μg/kg in flesh and 0.3-5.6μg/kg in pits). However, soil arsenic concentrations are frequently elevated to far above recommended levels and arsenic uptake in faster growing plants has to be assessed. Copyright © 2011 Elsevier B.V. All rights reserved.

Spatial Modeling of Iron Transformations Within Artificial Soil Aggregates

NASA Astrophysics Data System (ADS)

Kausch, M.; Meile, C.; Pallud, C.

2008-12-01

Structured soils exhibit significant variations in transport characteristics at the aggregate scale. Preferential flow occurs through macropores while predominantly diffusive exchange takes place in intra-aggregate micropores. Such environments characterized by mass transfer limitations are conducive to the formation of small-scale chemical gradients and promote strong spatial variation in processes controlling the fate of redox-sensitive elements such as Fe. In this study, we present a reactive transport model used to spatially resolve iron bioreductive processes occurring within a spherical aggregate at the interface between advective and diffusive domains. The model is derived from current conceptual models of iron(hydr)oxide (HFO) transformations and constrained by literature and experimental data. Data were obtained from flow-through experiments on artificial soil aggregates inoculated with Shewanella putrefaciens strain CN32, and include the temporal evolution of the bulk solution composition, as well as spatial information on the final solid phase distribution within aggregates. With all iron initially in the form of ferrihydrite, spatially heterogeneous formation of goethite/lepidocrocite, magnetite and siderite was observed during the course of the experiments. These transformations were reproduced by the model, which ascribes a central role to divalent iron as a driver of HFO transformations and master variable in the rate laws of the considered reaction network. The predicted dissolved iron breakthrough curves also match the experimental ones closely. Thus, the computed chemical concentration fields help identify factors governing the observed trends in the solid phase distribution patterns inside the aggregate. Building on a mechanistic description of transformation reactions, fluid flow and solute transport, the model was able to describe the observations and hence illustrates the importance of small-scale gradients and dynamics of bioreductive processes for assessing bulk iron cycling. As HFOs are ubiquitous in soils, such process-level understanding of aggregate-scale iron dynamics has broad implications for the prediction of the subsurface fate of nutrients and contaminants that interact strongly with HFO surfaces.

A Reactive Transport Model for the Distribution and Age of Carbon in Soils and Sediments Through Direct Simulation of the Stable and Radiogenic Isotopologues

NASA Astrophysics Data System (ADS)

Druhan, J. L.; Lawrence, C. R.

2015-12-01

We present a reactive transport (RT) approach to link hydrologic transport, geochemical transformations and microbial activity influencing the magnitude and residence time of different carbon pools under variably saturated conditions. This model explicitly simulates the simultaneous transport, transformation, fractionation and decay of the three isotopes of carbon (12C, 13C and 14C) through a mechanistic framework. This is demonstrated with a modification of the CrunchTope multi-component RT software to extend the isotope-specific versions of both microbially-mediated and transition state theory (TST) rate laws to accommodate a three-isotope system. In addition both aqueous and solid phase decay of 14C are tracked, yielding in an implicit means of accounting for the 13C/12C correction in normalized radiocarbon ages. The capacity of this approach to quantify the storage and flux of carbon through subsurface compartments is demonstrated using two examples distinguished by timescale. The first considers a simplified flow path in which an influent containing labile organic carbon is distributed by biogenic reduction and mineralization into a suite of reaction products. The residence time of these pools and their characteristic stable isotope ratios are tracked through a variety of transient processes occurring at short timescales (e.g. months). These include a change in fluid flow rate, a limitation of ammonium supporting anabolic growth and an influx of oxygenated fluid. The second example considers the distribution of carbon over the timescale of soil development (e.g., millennia), using a dataset of stable isotope ratios and radiocarbon ages of organic and inorganic carbon present in both dissolved and solid phases from a soil chronosequence near Santa Cruz, CA. The results of these model simulations suggest the promise of this tool for improving our understanding of coupling between hydrologic transport and biogeochemical reactions in soils.

2H and 18O depletion of water close to organic surfaces

NASA Astrophysics Data System (ADS)

Chen, Guo; Auerswald, Karl; Schnyder, Hans

2016-06-01

Hydrophilic surfaces influence the structure of water close to them and may thus affect the isotope composition of water. Such an effect should be relevant and detectable for materials with large surface areas and low water contents. The relationship between the volumetric solid : water ratio and the isotopic fractionation between adsorbed water and unconfined water was investigated for the materials silage, hay, organic soil (litter), filter paper, cotton, casein and flour. Each of these materials was equilibrated via the gas phase with unconfined water of known isotopic composition to quantify the isotopic difference between adsorbed water and unconfined water. Across all materials, isotopic fractionation was significant (p<0.05) and negative (on average -0.91 ± 0.22 ‰ for 18/16O and -20.6 ± 2.4 ‰ for 2/1H at an average solid : water ratio of 0.9). The observed isotopic fractionation was not caused by solutes, volatiles or old water because the fractionation did not disappear for washed or oven-dried silage, the isotopic fractionation was also found in filter paper and cotton, and the fractionation was independent of the isotopic composition of the unconfined water. Isotopic fractionation became linearly more negative with increasing volumetric solid : water ratio and even exceeded -4 ‰ for 18/16O and -44 ‰ for 2/1H. This fractionation behaviour could be modelled by assuming two water layers: a thin layer that is in direct contact and influenced by the surface of the solid and a second layer of varying thickness depending on the total moisture content that is in equilibrium with the surrounding vapour. When we applied the model to soil water under grassland, the soil water extracted from 7 and 20 cm depth was significantly closer to local meteoric water than without correction for the surface effect. This study has major implications for the interpretation of the isotopic composition of water extracted from organic matter, especially when the volumetric solid : water ratio is larger than 0.5 or for processes occurring at the solid-water interface.

Kinetic modelling of a diesel-polluted clayey soil bioremediation process.

PubMed

Fernández, Engracia Lacasa; Merlo, Elena Moliterni; Mayor, Lourdes Rodríguez; Camacho, José Villaseñor

2016-07-01

A mathematical model is proposed to describe a diesel-polluted clayey soil bioremediation process. The reaction system under study was considered a completely mixed closed batch reactor, which initially contacted a soil matrix polluted with diesel hydrocarbons, an aqueous liquid-specific culture medium and a microbial inoculation. The model coupled the mass transfer phenomena and the distribution of hydrocarbons among four phases (solid, S; water, A; non-aqueous liquid, NAPL; and air, V) with Monod kinetics. In the first step, the model simulating abiotic conditions was used to estimate only the mass transfer coefficients. In the second step, the model including both mass transfer and biodegradation phenomena was used to estimate the biological kinetic and stoichiometric parameters. In both situations, the model predictions were validated with experimental data that corresponded to previous research by the same authors. A correct fit between the model predictions and the experimental data was observed because the modelling curves captured the major trends for the diesel distribution in each phase. The model parameters were compared to different previously reported values found in the literature. Pearson correlation coefficients were used to show the reproducibility level of the model. Copyright © 2016. Published by Elsevier B.V.

Development of a pressurized liquid extraction-solid-phase extraction followed by liquid chromatography-electrospray ionization tandem mass spectrometry method for the quantitative determination of benzoxazolinones and their degradation products in agricultural soil.

PubMed

Villagrasa, M; Guillamón, M; Navarro, A; Eljarrat, E; Barceló, D

2008-02-01

A new analytical method for the quantitative determination of benzoxazolinones and their degradation products in agricultural soils based on the use of pressurized liquid extraction (PLE) followed by solid-phase extraction (SPE) and then instrumental determination using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS) is described. Using this method, the characterization, separation and quantitative detection of a mixture of two benzoxazolinones, benzoxazolin-2-one (BOA) and 6-methoxybenzoxazolin-2-one (MBOA) and their degradation products, 2-aminophenol (APH), N-(2-hydroxyphenyl)malonamic acid (HMPMA), 2-amino-3-H-phenoxazin-3-one (APO), 9-methoxy-2-amino-3-H-phenoxazin-3-one (AMPO), 2-acetylamino-3-H-phenoxazin-3-one (AAPO) and 2-acetylamino-9-methoxy-2-amino-3-H-phenoxazin-3-one (AAMPO) was achieved. The complete LC-ESI-MS-MS precursor-product ion fragmentation pathways for the degradation products of benzoxazolinones are described for the first time. Quantitative analysis was done in the multiple reaction mode using two specific combinations of precursor-product ion transitions for each compound. The optimized method was quality assessed by the measure of parameter as recovery, linearity, sensitivity, repeatability and reproducibility. Recoveries of the analytes ranged from 53 to 123%. The developed method offered improvements to the sensitivity as compared with our previously LC-MS method, with detection limits down to 2.4-21 ng/g of dry weight. This achievement allows us to identify and quantify for the first time degradation products of benzoxazolinones in real agricultural soil samples. Analytes were found in the range of 20.6-149 ng/g dry weight.

Moessbauer Mineralogy on the Moon: The Lunar Regolith

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Korotev, Randy L..; Shelfer, Tad D.; Klingelhoefer, Goestar

1997-01-01

A first-order requirement for spacecraft missions that land on solid planetary objects is instrumentation for mineralogical analyses. For purposes of providing diagnostic information about naturally-occurring materials, the element iron is particularly important because it is abundant and multivalent. Knowledge of the oxidation state of iron and its distribution among iron-bearing mineralogies tightly constrains the types of materials present and provides information about formation and modification (weathering) processes. Because Moessbauer spectroscopy is sensitive to both the valence of iron and its local chemical environment, the technique is unique in providing information about both the relative abundance of iron-bearing phases and oxidation state of the iron. The Moessbauer mineralogy of lunar regolith samples (primarily soils from the Apollo 16 and 17 missions to the Moon) were measured in the laboratory to demonstrate the strength of the technique for in situ mineralogical exploration of the Moon. The regolith samples were modeled as mixtures of five iron-bearing phases: olivine, pyroxene, glass, ilmenite, and metal. Based on differences in relative proportions of iron associated with these phases, volcanic ash regolith can be distinguished from impact-derived regolith, impact-derived soils of different geologic affinity (e.g., highlands, maria) can be distinguished on the basis of their constituent minerals, and soil maturity can be estimated. The total resonant absorption area of the Moessbauer spectrum can be used to estimate total FeO concentrations.

Evaluation of the slurry management strategy and the integration of the composting technology in a pig farm - Agronomical and environmental implications.

PubMed

Sáez, José A; Clemente, Rafael; Bustamante, M Ángeles; Yañez, David; Bernal, M Pilar

2017-05-01

The changes in livestock production systems towards intensification frequently lead to an excess of manure generation with respect to the agricultural land available for its soil application. However, treatment technologies can help in the management of manures, especially in N-surplus areas. An integrated slurry treatment system based on solid-liquid separation, aerobic treatment of the liquid and composting the solid fraction was evaluated in a pig farm (sows and piglets) in the South of Spain. Solid fraction separation using a filter band connected to a screw press had low efficiency (38%), which was greatly improved incorporating a rotatory sieve (61%). The depuration system was very efficient for the liquid, with total removal of 84% total solids, 87% volatile solids, and 98% phosphorus. Two composting systems were tested through mechanical turning of: 1- a mixture of solid fraction stored for 1 month after solid-liquid separation and cereal straw; 2- recently-separated solid fraction mixed with cotton gin waste. System 2 was recommended for the farm, as it exhibited a fast temperature rise and a long thermophilic phase to ensure compost sanitisation, and high recovery of nutrients (TN 77%, P and K > 85%) and organic matter (45%). The composts obtained were mature, stable and showed a high degree of humification of their organic matter, absence of phytotoxicity and concentrations of nutrients similar to other composts from pig manure or separated slurry solids. However, the introduction of slurry from piglets into the solid-liquid separation system should be avoided in order to reduce the content of Zn in the compost, which lowers its quality. The slurry separation followed by composting of the solid fraction using a passive windrow system, and aeration of the liquid phase, was the most recommendable procedure for the reduction of GHG emissions on the farm. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of biochars produced from solid organic municipal waste on soil quality parameters.

PubMed

Randolph, P; Bansode, R R; Hassan, O A; Rehrah, Dj; Ravella, R; Reddy, M R; Watts, D W; Novak, J M; Ahmedna, M

2017-05-01

New value-added uses for solid municipal waste are needed for environmental and economic sustainability. Fortunately, value-added biochars can be produced from mixed solid waste, thereby addressing solid waste management issues, and enabling long-term carbon sequestration. We hypothesize that soil deficiencies can be remedied by the application of municipal waste-based biochars. Select municipal organic wastes (newspaper, cardboard, woodchips and landscaping residues) individually or in a 25% blend of all four waste streams were used as feedstocks of biochars. Three sets of pyrolysis temperatures (350, 500, and 750 °C) and 3 sets of pyrolysis residence time (2, 4 and 6 h) were used for biochar preparation. The biochar yield was in the range of 21-62% across all feedstocks and pyrolysis conditions. We observed variations in key biochar properties such as pH, electrical conductivity, bulk density and surface area depending on the feedstocks and production conditions. Biochar increased soil pH and improved its electrical conductivity, aggregate stability, water retention and micronutrient contents. Similarly, leachate from the soil amended with biochar showed increased pH and electrical conductivity. Some elements such as Ca and Mg decreased while NO 3 -N increased in the leachates of soils incubated with biochars. Overall, solid waste-based biochar produced significant improvements to soil fertility parameters indicating that solid municipal wastes hold promising potential as feedstocks for manufacturing value-added biochars with varied physicochemical characteristics, allowing them to not only serve the needs for solid waste management and greenhouse gas mitigation, but also as a resource for improving the quality of depleted soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of macro-scale soil properties from pore-scale structures: model derivation.

PubMed

Daly, K R; Roose, T

2018-01-01

In this paper, we use homogenization to derive a set of macro-scale poro-elastic equations for soils composed of rigid solid particles, air-filled pore space and a poro-elastic mixed phase. We consider the derivation in the limit of large deformation and show that by solving representative problems on the micro-scale we can parametrize the macro-scale equations. To validate the homogenization procedure, we compare the predictions of the homogenized equations with those of the full equations for a range of different geometries and material properties. We show that the results differ by [Formula: see text] for all cases considered. The success of the homogenization scheme means that it can be used to determine the macro-scale poro-elastic properties of soils from the underlying structure. Hence, it will prove a valuable tool in both characterization and optimization.

PAHs contamination in urban soils from Lisbon: spatial variability and potential risks

NASA Astrophysics Data System (ADS)

Cachada, Anabela; Pereira, Ruth; Ferreira da Silva, Eduardo; Duarte, Armando

2015-04-01

Polycyclic Aromatic hydrocarbons (PAHs) can become major contaminants in urban and industrial areas, due to the existence of a plethora of diffuse and point sources. Particularly diffuse pollution, which is normally characterized by continuous and long-term emission of contaminants below risk levels, can be a major problem in urban areas. Since PAHs are persistent and tend to accumulate in soils, levels are often above the recommended guidelines indicating that ecological functions of soils may be affected. Moreover, due to the lipophilic nature, hydrophobicity and low chemical and biological degradation rates of PAHs, which leads to their bioconcentration and bioamplification, they may reach toxicological relevant concentrations in organisms. The importance and interest of studying this group of contaminants is magnified due to their carcinogenic, mutagenic and endocrine disrupting effects. In this study, a risk assessment framework has been followed in order to evaluate the potential hazards posed by the presence of PAHs in Lisbon urban soils. Hence, the first step consisted in screening the total concentrations of PAHs followed by the calculation of risks based on existing models. Considering these models several samples were identified as representing a potential risk when comparing with the guidelines for soil protection. Moreover, it was found that for 38% of samples more than 50% of species can be potentially affected by the mixture of PAHs. The use of geostatistical methods allowed to visualize the predicted distribution of PAHs in Lisbon area and identify the areas where possible risk to the environment are likely occurring However, it is known that total concentration may not allow a direct prediction of environmental risk, since in general only a fraction of total concentration is available for partitioning between soil and solution and thus to be uptake or transformed by organisms (bioacessible or bioavailable) or to be leached to groundwater. The reason is that once PAHs reach the soils, they can be incorporated into more stable solid phases over time, for instance, they can be retained in the organic phase, and this process known as aging, can be virtually irreversible. This phenomenon can be particularly relevant in urban soils since the highest levels are normally found in historical sites, suggesting a long-term accumulation as observed in the present study. The estimation of this fraction is traditionally performed by using bioassays (bioavailability), yet chemical methods can also be used (chemical availability). Following a higher tier of the risk assessment framework, some selected samples previously identified as representing a potential hazard were tested for their bioavailability (earthworm bioaccumulation assay, OECD test n° 317) and chemical availability (solid phase extraction with Tenax® and water). Results showed that in spite of the very high levels found in some samples, the risks can be negligible, since both the bioavailable and water soluble fractions were very low. The relationship between available fraction and soil properties is not clear, and differences observed between samples are probably related to the age of contamination since lower available fractions were observed in the most contaminated soils.

Rapid and sensitive Nitrosomonas europaea biosensor assay for quantification of bioavailable ammonium sensu strictu in soil.

PubMed

Nguyen, Minh Dong; Risgaard-Petersen, Nils; Sørensen, Jan; Brandt, Kristian K

2011-02-01

Knowledge on bioavailable ammonium sensu strictu (i.e., immediately available for cellular uptake) in soil is required to understand nutrient uptake processes in microorganisms and thus of vital importance for plant production. We here present a novel ammonium biosensor approach based on the lithoautotrophic ammonia-oxidizing bacterium Nitrosomonas europaea transformed with a luxAB sensor plasmid. Bioluminescence-based ammonium detection was achieved within 10 min with a quantification limit in liquid samples of ∼20 μM and a linear response range up to 400 μM. Biosensor and conventional chemical quantification of ammonium in soil solutions agreed well across a range of sample and assay conditions. The biosensor was subsequently applied for a solid phase-contact assay allowing for direct interaction of biosensor cells with soil particle-associated (i.e., exchangeable plus fixed) ammonium. The assay successfully quantified bioavailable ammonium even in unfertilized soil and demonstrated markedly higher ratios of bioavailable ammonium to water- or 2 M KCl-exchangeable ammonium in anoxic soil than in corresponding oxic soil. Particle-associated ammonium contributed by at least 74% and 93% of the total bioavailable pool in oxic and anoxic soil, respectively. The N. europaea biosensor should have broad relevance for environmental monitoring of bioavailable ammonium and processes depending on ammonium bioavailability.

Iron cycling under oscillatory redox conditions: from observations to processes

NASA Astrophysics Data System (ADS)

Meile, C. D.; Chen, C.; Barcellos, D.; Wilmoth, J.; Thompson, A.

2017-12-01

Fe oxyhydroxides play a critical role in soils through their role as structural entities, their high sorption capacity, their role as terminal electron acceptors in the respiration of organic matter, as well as their potential to affect the reactivity of that organic matter. In soils that undergo repeated fluctuations in O2 concentrations, soil iron undergoes transformations between reduced and oxidized forms. The rate of Fe(II) oxidation can govern the nature of Fe(III) oxyhydroxides formed, and hence can affect rates of OC mineralization under suboxic conditions. But it remains unclear if this same behavior occurs in soils, where Fe(II) is mainly present as surface complexes. We documented the impact of such redox oscillations on iron cycling through targeted experiments, in which the magnitude and frequency of redox oscillations were varied systematically on soils from the Luquillo Critical Zone Observatory, Puerto Rico. Our observations demonstrated that higher O2 concentrations led to a faster Fe(II) oxidation and resulted in less crystalline Fe(III)-oxyhydroxides than lower O2 concentrations. We further studied the dynamics of iron phases by amending soil slurries with isotopically-labeled 57Fe(II) and developed a numerical model to quantify the individual processes. Our model showed a higher rate of Fe(III) reduction and increased sorption capacity following the oxidation of Fe(II) at high O2 levels than at low O2 levels, and revealed rapid Fe atom exchange between solution and solid phase. Concurrent measurements of CO2 in our oscillation experiments further illustrated the importance O2 fluctuations on coupled Fe-C dynamics.

Spatiotemporal dynamics of phosphorus release, oxygen consumption and greenhouse gas emissions after localised soil amendment with organic fertilisers.

PubMed

Christel, Wibke; Zhu, Kun; Hoefer, Christoph; Kreuzeder, Andreas; Santner, Jakob; Bruun, Sander; Magid, Jakob; Jensen, Lars Stoumann

2016-06-01

Organic fertilisation inevitably leads to heterogeneous distribution of organic matter and nutrients in soil, i.e. due to uneven surface spreading or inhomogeneous incorporation. The resulting localised hotspots of nutrient application will induce various biotic and abiotic nutrient turnover processes and fixation in the residue sphere, giving rise to distinct differences in nutrient availability, soil oxygen content and greenhouse gas (GHG) production. In this study we investigated the spatiotemporal dynamics of the reaction of manure solids and manure solids char with soil, focusing on their phosphorus (P) availability, as current emphasis on improving societal P efficiency through recycling waste or bio-based fertilisers necessitates a sound understanding of their behaviour. Soil layers amended at a constant P application rate with either pig manure solids or char made from pig manure solids were incubated for three weeks between layers of non-amended, P-depleted soil. Spatial and temporal changes in and around the amendment layers were simultaneously investigated in this study using a sandwich sensor consisting of a planar oxygen optode and multi-element diffusive gradients in thin films (DGT) gels, combined with GHG emission measurements. After three weeks of incubation, the soil containing a layer amended with manure solids had a lower overall O2 content and had emitted significantly more CO2 than the non-amended control or the char-amended soil. The P availability from manure solids was initially higher than that from the char, but decreased over time, whereas from the char-amended layer P availability increased in the same period. In both treatments, increases in P availability were confined to the amended soil layer and did not greatly affect P availability in the directly adjacent soil layers during the three-week incubation. These results highlight the importance of placing organic P fertilisers close to where the plant roots will grow in order to facilitate optimal fertiliser use efficiency. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Genome Sequence of Lysinibacillus sphaericus, a Lignin-Degrading Bacterium Isolated from Municipal Solid Waste Soil.

PubMed

Persinoti, Gabriela F; Paixão, Douglas A A; Bugg, Timothy D H; Squina, Fabio M

2018-05-03

We report here the draft genome sequence of Lysinibacillus sphaericus strain A1, a potential lignin-degrading bacterium isolated from municipal solid waste (MSW) soil and capable of enhancing gas release from lignocellulose-containing soil. Copyright © 2018 Persinoti et al.

AN IN VITRO GASTROINTESTINAL METHOD TO ESTIMATE BIOAVAILABLE ARSENIC IN CONTAMINATED SOILS AND SOLID MEDIA. (R825410)

EPA Science Inventory

A method was developed to simulate the human gastrointestinal environment and
to estimate bioavailability of arsenic in contaminated soil and solid media. In
this in vitro gastrointestinal (IVG) method, arsenic is sequentially extracted
from contaminated soil with ...

Mixed functional monomers-based monolithic adsorbent for the effective extraction of sulfonylurea herbicides in water and soil samples.

PubMed

Pei, Miao; Zhu, Xiangyu; Huang, Xiaojia

2018-01-05

Effective extraction is a key step in the determination of sulfonylurea herbicides (SUHs) in complicated samples. According to the chemical properties of SUHs, a new monolithic adsorbent utilizing acrylamidophenylboronic acid and vinylimidazole as mixed functional monomers was synthesized. The new adsorbent was employed as the extraction phase of multiple monolithic fiber solid-phase microextraction (MMF-SPME) of SUHs, and the extracted SUHs were determined by high-performance liquid chromatography with diode array detection (HPLC-DAD). Results well evidence that the prepared adsorbent could extract SUHs in environmental waters and soil effectively through multiply interactions such as boronate affinity, dipole-dipole and π-π interactions. Under the optimized extraction conditions, the limits of detection for target SUHs in environmental water and soil samples were 0.018-0.17μg/L and 0.14-1.23μg/kg, respectively. At the same time, the developed method also displayed some analytical merits including wide linear dynamic ranges, good method reproducibility, satisfactory sensitivity and low consume of organic solvent. Finally, the developed were successfully applied to monitor trace SUHs in environmental water and soil samples. The recoveries at three fortified concentrations were in the range of 70.6-119% with RSD below 11% in all cases. The obtained results well demonstrate the excellent practical applicability of the developed MMF-SPME-HPLC-DAD method for the monitoring of SUHs in water and soil samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

DOE PAGES

Hausladen, Debra M.; Fendorf, Scott

2017-01-13

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$-$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH) 3- and Cr 0.25Fe 0.75(OH) 3-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregatesmore » simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.« less

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hausladen, Debra M.; Fendorf, Scott

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$-$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH) 3- and Cr 0.25Fe 0.75(OH) 3-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregatesmore » simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swift, Barry D.; Tarantino, Joseph J., P. E.

The Paducah Gaseous Diffusion Plant (PGDP), owned by the Department of Energy (DOE), has been enriching uranium since the early 1950s. The enrichment process involves electrical and mechanical components that require periodic cleaning. The primary cleaning agent was trichloroethene (TCE) until the late 1980s. Historical documentation indicates that a mixture of TCE and dry ice were used at PGDP for testing the integrity of steel cylinders, which stored depleted uranium. TCE and dry ice were contained in a below-ground pit and used during the integrity testing. TCE seeped from the pit and contaminated the surrounding soil. The Lasagna{trademark} technology wasmore » identified in the Record of Decision (ROD) as the selected alternative for remediation of the cylinder testing site. A public-private consortium formed in 1992 (including DOE, the U.S. Environmental Protection Agency, and the Kentucky Department for Environmental Protection, Monsanto, DuPont, and General Electric) developed the Lasagna{trademark} technology. This innovative technology employs electrokinetics to remediate soil contaminated with organics and is especially suited to sites with low permeability soils. This technology uses direct current to move water through the soil faster and more uniformly than hydraulic methods. Electrokinetics moves contaminants in soil pore water through treatment zones comprised of iron filings, where the contaminants are decomposed to basic chemical compounds such as ethane. After three years of development in the laboratory, the consortium field tested the Lasagna{trademark} process in several phases. CDM installed and operated Phase I, the trial installation and field test of a 150-square-foot area selected for a 120-day run in 1995. Approximately 98 percent of the TCE was removed. CDM then installed and operated the next phase (IIa), a year-long test on a 600-square-foot site. Completed in July 1997, this test removed 75 percent of the total volume of TCE down to a depth of 45 feet. TCE in the test sites. Based on the successful field tests (Phases I and IIa), the ROD was prepared and the Lasagna{trademark} alternative was selected for remediation of TCE contaminated soils at the cylinder testing site Solid Waste Management Unit 91(SWMU 91). Bechtel Jacobs Company LLC contracted CDM to construct and operate a full-scale Lasagna{trademark} remediation system at the site (Phase IIb). Construction began in August 1999 and the operational phase was initiated in December 1999. The Lasagna{trademark} system was operated for two years and reduced the average concentration of TCE in SWMU 91 soil from 84 ppm to less than 5.6 ppm. Verification sampling was conducted during May, 2002. Results of the verification sampling indicated the average concentration of TCE in SWMU 91 soil was 0.38 ppm with a high concentration of 4.5 ppm.« less

Water retention of repellent and subcritical repellent soils: New insights from model and experimental investigations

NASA Astrophysics Data System (ADS)

Czachor, H.; Doerr, S. H.; Lichner, L.

2010-01-01

SummarySoil organic matter can modify the surface properties of the soil mineral phase by changing the surface tension of the mineral surfaces. This modifies the soil's solid-water contact angle, which in turn would be expected to affect its water retention curve (SWRC). Here we model the impact of differences in the soil pore-water contact angle on capillarity in non-cylindrical pores by accounting for their complex pore geometry. Key outcomes from the model include that (i) available methods for measuring the Young's wetting angle on soil samples are insufficient in representing the wetting angle in the soil pore space, (ii) the wetting branch of water retention curves is strongly affected by the soil pore-water contact angle, as manifest in the wetting behavior of water repellent soils, (iii) effects for the drying branch are minimal, indicating that both wettable and water repellent soils should behave similarly, and (vi) water retention is a feature not of only wettable soils, but also soils that are in a water repellent state. These results are tested experimentally by determining drying and wetting branches for (a) 'model soil' (quartz sands with four hydrophobization levels) and (b) five field soil samples with contrasting wettability, which were used with and without the removal of the soil organic matter. The experimental results support the theoretical predictions and indicate that small changes in wetting angle can cause switches between wettable and water repellent soil behavior. This may explain the common observation that relatively small changes in soil water content can cause substantial changes in soil wettability.

Partition coefficient of cadmium between organic soils and bean and oat plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siddqui, M.F.R.; Courchesne, F.; Kennedy, G.

Environmental fate models require the partition coefficient data of contaminants among two or more environmental compartments. The bioaccumulation of cadmium (Cd) by bean and oat plants grown on organic soils in a controlled growth chamber was investigated to validate the plant/soil partition coefficient. Total Cd was measured in the soils and in the different parts of the plants. The mean total Cd concentrations for soil cultivated with beans and oats were 0.86 and 0.69 {micro}g/g, respectively. Selective extractants (BaCl{sub 2}, Na-pyrophosphate and HNO{sub 3}-hydroxy) were used to evaluate solid phase Cd species in the soil. In the soil cultivated withmore » bean, BaCl{sub 2} exchangeable, Na-pyrophosphate extractable and HNO{sub 3}-NH{sub 2}OH extractable Cd represented 1.2, 1.6 and 50.9% of total soil Cd, respectively. For the soil cultivated with oats, the same extractants gave values of 1.1, 1.8 and 61.9%. Cd concentration levels in bean plants followed the sequence roots > fruits = stems > leaves (p < 0.01) while the following sequence was observed for oat plants: roots > fruits > stems > leaves (p < 0.05). The partition coefficient for total Cd (Cd{sub Plant tissue}/Cd{sub Soil}) was in the range of 0.28--0.55 for bean plants and 1.03--1.86 for oat plants.« less

Comparison of soil solution speciation and diffusive gradients in thin-films measurement as an indicator of copper bioavailability to plants.

PubMed

Zhao, Fang-Jie; Rooney, Corinne P; Zhang, Hao; McGrath, Steve P

2006-03-01

The toxicity effect concentrations (10% effective concentration [EC10] and 50% effective concentration [EC50]) of total added Cu derived from barley root elongation and tomato growth assays varied widely among 18 European soils. We investigated whether this variation could be explained by the solubility or speciation of Cu in soil solutions or the diffusive gradients in thin-films (DGT) measurement. Solubility and Cu speciation varied greatly among the soils tested. However, the EC10 and EC50 of soil solution Cu or free Cu2+ activity varied even more widely than those based on the total added Cu, indicating that solubility or soil solution speciation alone could not explain intersoil variation in Cu toxicity. Estimated EC10 and EC50 of free Cu2+ activity correlated closely and negatively with soil pH, indicating a protective effect of H+, which is consistent with the biotic ligand model concept. The DGT measurement was found to narrow the intersoil variation in EC50 considerably and to be a better predictor of plant Cu concentrations than either soil solution Cu or free Cu2+ activity. We conclude that plant bioavailability of Cu in soil depends on Cu speciation, interactions with protective ions (particularly H+), and the resupply from the solid phase, and we conclude that the DGT measurement provides a useful indicator of Cu bioavailability in soil.

QSAR development and bioavailability determination: the toxicity of chloroanilines to the soil dwelling springtail Folsomia candida.

PubMed

Giesen, Daniel; van Gestel, Cornelis A M

2013-03-01

Quantitative structure-activity relationships (QSARs) are an established tool in environmental risk assessment and a valuable alternative to the exhaustive use of test animals under REACH. In this study a QSAR was developed for the toxicity of a series of six chloroanilines to the soil-dwelling collembolan Folsomia candida in standardized natural LUFA2.2 soil. Toxicity endpoints incorporated in the QSAR were the concentrations causing 10% (EC10) and 50% (EC50) reduction in reproduction of F. candida. Toxicity was based on concentrations in interstitial water estimated from nominal concentrations in the soil and published soil-water partition coefficients. Estimated effect concentrations were negatively correlated with the lipophilicity of the compounds. Interstitial water concentrations for both the EC10 and EC50 for four compounds were determined by using solid-phase microextraction (SPME). Measured and estimated concentrations were comparable only for tetra- and pentachloroaniline. With decreasing chlorination the disparity between modelled and actual concentrations increased. Optimisation of the QSAR therefore could not be accomplished, showing the necessity to move from total soil to (bio)available concentration measurements. Copyright © 2012 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, W.; Kan, A.T.; Fu, G.

Neutral organic contaminants commonly reside on the solid portion of soils and sediments. The extent of desorption from these solids determines the fate, reactivity, and toxicity. Numerous researchers have observed that, after an initial exposure of a few days, desorption takes place in two phases, namely, an initial rapid release followed by a long-term resistant phase. Resistant desorption has been highly unpredictable. In this research, the adsorption and desorption of chlorobenzenes, hexachlorobutadiene, and naphthalene have been studied using historically and freshly contaminated bayou sediments from Lake Charles, Louisiana, USA. After an initial release period, both laboratory-spiked and historically contaminated sedimentsmore » from Lake Charles, Louisiana, USA. After an initial release period, both laboratory-spiked and historically contaminated sediments exhibit similar desorption profiles. The simulations compare favorably with previous in situ measurements. All desorption results, both laboratory and field, could reasonably be interpreted using a single irreversible isotherm. Consequences of these results in terms of sediment quality criteria (SQC) are also discussed. Finally, an index of fractional irreversible adsorption is proposed and tested.« less

Adsorption of phenanthrene on activated carbon increases mineralization rate by specific bacteria.

PubMed

Leglize, Pierre; Alain, Saada; Jacques, Berthelin; Corinne, Leyval

2008-03-01

Bioavailability of polycyclic aromatic hydrocarbons (PAH) in soil is affected by PAH sorption to solid phase. We studied the influence of activated carbon (AC) on phenanthrene (PHE) mineralization by five degrading bacterial strains isolated from contaminated soil. PHE adsorption on AC was important and reduced PHE aqueous concentration up to 90%. PHE degradation was improved in the presence of activated carbon with three of the bacterial strains, named NAH1, MATE3 and MATE7, which produced biofilms, whereas it was not improved with the two other ones, which did not produce biofilms, MATE10 and MATE12. Monitoring PHE distribution during incubation showed that aqueous PHE concentration was significantly higher with the biofilm-producing NAH1 than with MATE10. Bacterial adhesion on AC was also investigated. The precoating of AC with PHE increased NAH1 and MATE3 adhesion to the solid surface (>16 and >13%, respectively). Bacterial properties, such as biofilm production and adhesion to AC capacity seemed to be related to their ability to optimize PHE degradation by improving PHE diffusion and reducing diffusion path length.

Large-scale model of flow in heterogeneous and hierarchical porous media

NASA Astrophysics Data System (ADS)

Chabanon, Morgan; Valdés-Parada, Francisco J.; Ochoa-Tapia, J. Alberto; Goyeau, Benoît

2017-11-01

Heterogeneous porous structures are very often encountered in natural environments, bioremediation processes among many others. Reliable models for momentum transport are crucial whenever mass transport or convective heat occurs in these systems. In this work, we derive a large-scale average model for incompressible single-phase flow in heterogeneous and hierarchical soil porous media composed of two distinct porous regions embedding a solid impermeable structure. The model, based on the local mechanical equilibrium assumption between the porous regions, results in a unique momentum transport equation where the global effective permeability naturally depends on the permeabilities at the intermediate mesoscopic scales and therefore includes the complex hierarchical structure of the soil. The associated closure problem is numerically solved for various configurations and properties of the heterogeneous medium. The results clearly show that the effective permeability increases with the volume fraction of the most permeable porous region. It is also shown that the effective permeability is sensitive to the dimensionality spatial arrangement of the porous regions and in particular depends on the contact between the impermeable solid and the two porous regions.

The Impact of Fire on Mercury Cycling in Watershed Systems

NASA Astrophysics Data System (ADS)

Lopez, S.; Mendez, C.; Hogue, T.; Jay, J.

2006-12-01

Mercury methylation is a process by which the less-toxic inorganic mercury is transformed into methylmercury (MeHg). MeHg is a potent neurotoxin with a strong tendency to biomagnify within the food chain. Limited studies suggest that wildfires change the soil characteristics and contribute to Hg transport and possibly methylation in downstream ecosystems. We propose that post-fire Hg cycling can be related to various soil properties and burn characteristics. In order to better understand the effects of wildfires on Hg cycling, studies were undertaken within a burned watershed and a neighboring unburned site, Malibu Creek and Cold Creek, respectively. Soil sampling of the burned and control (unburned) regions were composed of 25 square foot grids with nine equidistant sampling points. Sediment samples for soil sieve analysis were collected at all grid points to determine the particle size distribution of the fine and coarse grain aggregates. Total Hg sediments were collected from the three middle points of the grid at two soil horizons to provide a vertical profile. Total Hg concentrations of the sediment samples were measured using the Direct Mercury Analyzer (DMA80). Initial analysis of the soil profiles reveals a decrease in Hg concentration at the soil surface (89 percent loss). Preliminary results indicate sites with the lowest concentration of Hg are characterized by a higher percentage of finer grain aggregates. Runoff from the first post-fire storm was extremely turbid and dark gray in color due to high levels of suspended solids (3980 mg/L). Total Hg concentrations in unfiltered and filtered samples (0.2 micron) were 196 and 4.7 ng/L, respectively, compared to the control which had unfiltered and filtered Hg levels of 6.1 and 2.3 ng/L, respectively, and 450 mg/L total suspended solids. The concentration of Hg on the particles was six times higher than the Hg content of suspended particles at the control site. Results also show much stronger partitioning (three-fold higher Kd's) to the solid phase in the fire- impacted site. On-going work includes: 1) analysis of Hg and ancillary geochemical parameters overlying water and porewater from samples collected in the streambed downstream of the fire, 2) analysis of Hg concentrations in various particle size fractions of soil; and 3) preliminary characterization of recovery through analysis of soil properties and Hg levels at the burned and control sites, one-year post-fire.

Distribution and speciation of ambient selenium in contrasted soils, from mineral to organic rich.

PubMed

Tolu, Julie; Thiry, Yves; Bueno, Maïté; Jolivet, Claudy; Potin-Gautier, Martine; Le Hécho, Isabelle

2014-05-01

Selenium adsorption onto oxy-hydroxides mainly controls its mobility in volcanic soils, red earths and soils poor in organic matter (OM) while the influence of OM was emphasized in podzol and peat soils. This work aims at deciphering how those solid phases influence ambient Se mobility and speciation under less contrasted conditions in 26 soils spanning extensive ranges of OM (1-32%), Fe/Al oxy-hydroxides (0.3-6.1%) contents and pH (4.0-8.3). The soil collection included agriculture, meadow and forest soils to assess the influence of OM quality as well. Trace concentrations of six ambient Se species (Se(IV), Se(VI) and 4 organo-Se compounds) were analyzed by HPLC-ICP-MS in three extractants (ultrapure water, phosphate and sodium hydroxide) targeting Se associated to different soil phases. The Kd values determined from ultrapure water extraction were higher than those reported in commonly used short-term experiments after Se-spiking. Correlations of ambient Se content and distribution with soil parameters explained this difference by an involvement of slow processes in Se retention in soils. The 26 Kd values determined here for a wide variety of soils thus represent a relevant database for long-term prediction of Se mobility. For soils containing less than 20% OM, ambient Se solubility is primarily controlled by its adsorption onto crystalline oxy-hydroxides. However, OM plays an important role in Se mobility by forming organo-mineral associations that may protect adsorbed Se from leaching and/or create anoxic zones (aggregates) where Se is immobilized after its reduction. Although for the first time, inorganic Se(IV), Se(VI) and organo-Se compounds were simultaneously investigated in a large soil collection, high Se proportions remain unidentified in each soil extract, most probably due to Se incorporation and/or binding to colloidal-sized OM. Variations of environmental factors regulating the extent of OM-mineral associations/aggregation may thus lead to changes in Se mobility and bio-availability. Copyright © 2014 Elsevier B.V. All rights reserved.

Selective Sorption of Dissolved Organic Carbon Compounds by Temperate Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jagadamma, Sindhu; Mayes, Melanie; Phillips, Jana Randolph

Physico-chemical sorption of dissolved organic carbon (DOC) on soil minerals is one of the major processes of organic carbon (OC) stabilization in soils, especially in deeper layers. The attachment of C on soil solids is related to the reactivity of the soil minerals and the chemistry of the sorbate functional groups, but the sorption studies conducted without controlling microbial activity may overestimate the sorption potential of soil. This study was conducted to examine the sorptive characteristics of a diverse functional groups of simple OC compounds (D-glucose, L-alanine, oxalic acid, salicylic acid, and sinapyl alcohol) on temperate climate soil orders (Mollisols,more » Ultisols and Alfisols) with and without biological degradative processes. Equilibrium batch experiments were conducted using 0-100 mg C L-1 at a solid-solution ratio of 1:60 for 48 hrs and the sorption parameters were calculated by Langmuir model fitting. The amount of added compounds that remained in the solution phase was detected by high performance liquid chromatography (HPLC) and total organic C (TOC) analysis. Soil sterilization was performed by -irradiation technique and experiments were repeated to determine the contribution of microbial degradation to apparent sorption. Overall, Ultisols did not show a marked preference for apparent sorption of any of the model compounds, as indicated by a narrower range of maximum sorption capacity (Smax) of 173-527 mg kg soil-1 across compounds. Mollisols exhibited a strong preference for apparent sorption of oxalic acid (Smax of 5290 mg kg soil-1) and sinapyl alcohol (Smax of 2031 mg kg soil-1) over the other compounds. The propensity for sorption of oxalic acid is mainly attributed to the precipitation of insoluble Ca-oxalate due to the calcareous nature of most Mollisol subsoils and its preference for sinapyl alcohol could be linked to the polymerization of this lignin monomer on 2:2 mineral dominated soils. The reactivity of Alfisols to DOC was in between that of Ultisols and Mollisols. HPLC results revealed significantly higher sorption of D-glucose and L-alanine than did TOC results, and duplicate experiments with sterilized soils confirmed that glucose and alanine were mineralized leading to higher apparent sorption values via HPLC. This study demonstrated that three common temperate soil orders experienced differential sorption of simple OC compounds, indicating that sorbate chemistry plays a significant role in the sorptive stabilization of DOC.« less

Assessment of Two Solid Anaerobic Digestate Soil Amendments for Effects on Soil Quality and Biosolarization Efficacy.

PubMed

Fernández-Bayo, Jesús D; Achmon, Yigal; Harrold, Duff R; McCurry, Dlinka G; Hernandez, Katie; Dahlquist-Willard, Ruth M; Stapleton, James J; VanderGheynst, Jean S; Simmons, Christopher W

2017-05-03

Anaerobic digestion is an organic waste bioconversion process that produces biofuel and digestates. Digestates have potential to be applied as soil amendment to improve properties for crop production including phytonutrient content and pest load. Our objective was to assess the impact of solid anaerobic digestates on weed seed inactivation and soil quality upon soil biosolarization (a pest control technique that combines solar heating and amendment-induced microbial activity). Two solid digestates from thermophilic (TD) and mesophilic (MD) digesters were tested. The solarized TD-amended samples presented significantly higher mortality of Brassica nigra (71%, P = 0.032) than its equivalent incubated at room temperature. However, biosolarization with digestate amendment led to decreased weed seed mortality in certain treatments. The plant-available water, total C, and extractable P and K were significantly increased (P < 0.05) in the incubated amended soils. The results confirm the potential of digestates as beneficial soil amendments. Further studies are needed to elucidate the impacts of digestate stability on biosolarization efficacy and soil properties.

Selective Separation and Determination of Heavy Metals (Cd, Pb, Cr) Speciation Forms from Hortic Antrosols

NASA Astrophysics Data System (ADS)

Bulgariu, D.; Bulgariu, L.

2009-04-01

The speciation, inter-phases distribution and biodisponibility of heavy metals in soils represent one of main problem of environmental geochemistry and agro-chemistry. This problem is very important in case of hortic antrosols (soils from glasshouses) for the elimination of agricultural products (fruits, vegetables) contamination with heavy metals. In soils from glass houses, the speciation and inter-phases distribution processes of heavy metals have a particular dynamic, different in comparison with those from non-protected soils. The predominant distribution forms of heavy metals in such soils types are: complexes with low mass organic molecules, organic-mineral complexes, complexes with inorganic ligands (hydroxide-complexes, carbonate-complexes, sulphate-complexes, etc.) and basic salts. All of these have high stabilities in conditions of soils from glass houses, and in consequence, the separation and determination of speciation forms (which is directly connected with biodisponibility of heavy metals) by usual methods id very difficult and has a high uncertain degree. In this study is presented an original method for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils, which is based by the combination of solid-liquid sequential extraction (SPE) with the extraction in aqueous polymer-inorganic salt two-phase systems (ABS). The soil samples used for this study have been sampled from three different locations (glass houses from Iasi, Barlad and Bacau - Romania) where the vegetables cultivation have bee performed by three different technologies. In this way was estimated the applicability and the analytical limits of method proposed by as, in function of the chemical-mineralogical and physical-chemical characteristics of soils. As heavy metals have been studied cadmium, lead and chromium, all being known for their high toxicity. The procedure used for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils has two main steps: (i) non-destructive separation of chemical-mineralogical associations and aggregates from soils samples - for this the separation method with heavy liquids (bromophorme) and isodynamic magnetic method have been used; (ii) sequential extraction of heavy metals from soil fractions separated in the first step, by using combined SPE-ABS procedure. For the preparation of combined extraction systems was used polyethylene glycol (with different molecular mass: 2000, 4000 and 8000). As phase-forming inorganic salts and as selective extracting agents we have used different usual inorganic reagents. The type and concentration of phase-forming salts have been selected in function of, both nature of extracted heavy metals and chemical-mineralogical characteristics of soil samples. The experimental parameters investigated in this study are: molecular mass of polyethylene glycol and the concentration of polymeric solutions, nature and concentration of phase-forming salts, nature and concentration of extracting agents, pH in extraction system phase, type of extracted heavy metals, type of speciation forms of heavy metals and their concentrations. All these factors can influence significantly the efficiency and the selectivity of separation process. The experimental results have indicate that the combined SPE-ABS extraction systems have better separation efficiency, in comparison with traditional SPE systems and ca realized a accurate discrimination between speciation forms of heavy metals from soils. Under these conditions, the estimation of inter-phases distribution and biodisponibility of heavy metals has a high precision. On the other hand, when the combined SPE-ABS systems are used, the concomitant extraction of the elements from the same geochemical association with studied heavy metals (inevitable phenomena in case of separation by SPE procedures) is significant diminished. This increases the separation selectivity and facilitated the more accurate determination of speciation forms concentration. By adequate selection of extraction conditions can be realized the selective separation of organic-mineral complexes, which will permit to perform detailed studies about the structure and chemical composition of these. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07).

Congener-specific extraction and separation of coplanar PCBs from soil using SPME and capillary GC/MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woolley, C.L.; Mani, V.; Shirey, R.E.

1995-12-31

The persistence and widespread environmental occurrence of polychlorinated biphenyls (PCBs) in the air, waterways and industrial facilities has created a need for quantitative and qualitative analysis of Aroclor-like mixtures. Although there are 209 possible PCB concerns, only a limited number have shown toxic activity similar to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The World Health Organization recently released a list of the 13 most toxic PCB congeners. Each was rated by its Toxic Equivalency Factor relative to TCDD. These 13 PCB congeners belong to the class of toxic coplanar compounds. These congeners commonly contain chlorosubstitutions in the 3,3{prime},4,4{prime} or 3,4,4{prime} or 3{prime},4,4{prime} positions andmore » either 0, 1, or 2 chloro-substituents in the ortho positions. A new capillary column containing a bonded octylmethyl polysiloxane stationary phase (SPB-Octyl) was evaluated for its propensity to separate coplanar PCB congeners. Solid phase microextraction (SPME), a solvent-free method for extracting volatiles and semi-volatiles from drinking water, waste water, soil and sludge was used to extract PCBs from soil. GC-ECD and GC-MS separations of PCB ladened soils were examined via SPME on the SPB-Octyl column. An approach for selective extraction of coplanar PCB congeners by SPME will be described.« less

Scattering of Microwaves by Steady-State Plasma Slabs, Columns, and Layers at Atmospheric Pressure

DTIC Science & Technology

1998-03-01

permeability unity is- (Fig 0) SÖ$ftS?S5 Pressure Plasmas Y=J7(er) . 2071 (1) where y is the complex propagation coefficient, w is the wave...a phase dependence expjtot-Yxl to a i„ ., permeability nnTty,^ J ’°SSy med’Um °f reIat<- ■j^r)^ • (1) where y is the complex propagation...preservation is an. issue. Some examples are food (solid or liquid) sterilization, pharmaceutical applications, and environmental applications ( soil

Fate and transport of mercury in soil systems : a numerical model in HP1 and sensitivity analysis

NASA Astrophysics Data System (ADS)

Leterme, Bertrand; Jacques, Diederik

2013-04-01

Mercury (Hg) poses threats for human health and the environment, notably due to its persistence and its ability to bioaccumulate in ecosystems. Anthropogenic activities are major contributors of mercury release to soils. Main sources of contamination include manufacturing (chlor-alkali plants, manometer spill), mine tailings from mercury, gold and silver mining industries, wood preservation. The objective of this study was to develop a reactive transport model for simulating mercury fate and transport in the unsaturated zone, and to gain insight in the fate and transport of Hg following anthropogenic soil contamination. The present work is done in the framework of the IMaHg project, which aims at providing recommendations to improve management of sites contaminated by mercury within the SNOWMAN funding framework. A model of mercury fate and transport in soil systems was developed using the reactive transport code HP1 (Jacques and Šimůnek, 2010). The geochemical database THERMODDEM (Blanc et al., 2012) is used, augmented with some speciation data from (Skyllberg, 2012). The main processes accounted for in the model are : Hg aqueous speciation (including complexation with dissolved organic matter (DOM) - humic and fulvic acids, and thiol groups), Hg sorption to solid organic matter (SOM), dissolution of solid phase Hg (e.g. cinnabar HgS(s)), dissolution of Hg non-aqueous liquid phase (NAPL), sunlight-driven Hg(II) reduction to Hg(0), Hg(0) diffusion in the gas phase and volatilization, DOM sorption to soil minerals. Colloid facilitated transport is implicitly accounted for by solute transport of Hg-DOM complexes. Because we focused on soil systems having a high Hg contamination, some processes showing relatively smaller Hg fluxes could be neglected such as vegetation uptake and atmospheric wet and dry deposition. NAPL migration and entrapment is not modelled, as pollution is assumed to be historical and only residual NAPL to be present. Mercury methylation and demethylation was not implemented, because it could be neglected in an oxidising environment. However, if the model is to be tested in more reducing conditions (e.g. shallow groundwater table), methyl- and dimethylmercury formation can be non negligible. Using 50 year time series of daily weather observations in Dessel (Belgium) and a typical sandy soil with deep groundwater (free drainage, oxic conditions), a sensitivity analysis was performed to assess the relative importance of processes and parameters within the model. We used the elementary effects method (Morris, 1991; Campolongo et al., 2007), which draws trajectories across the parameter space to derive information on the global sensitivity of the selected input parameters. The impact of different initial contamination phases (solid, NAPL, aqueous and combinations of these) was also tested. Simulation results are presented in terms of (i) Hg volatilized to the atmosphere; (ii) Hg leached out of the soil profile; (iii) Hg still present in the soil horizon originally polluted; and (iv) Hg still present in the soil profile but below the original contaminated horizon. Processes and parameters identified as critical based on the sensitivity analysis differ from one scenario to the other ; depending on pollution type (cinnabar, NAPL, aqueous Hg), on the indicator assessed and on time (after 5, 25 or 50 years). However, in general DOM in soil water was the most critical parameter. Other important parameters were those related to Hg sorption on SOM (thiols, and humic and fulvic acids), and to Hg complexation with DOM. Initial Hg concentration was also often identified as a sensitive parameter. Interactions between factors and non linear effects as measured by the elementary effect method were generally important, but also dependent on the type of contamination and on time. No model calibration was performed until now. The numerical tool could greatly benefit from partial model calibration and/or validation. Ideally, detailed speciation data on a contaminated sites would be required, together with a good characterization of the pollution source. References : Blanc, P., Lassin, A. and Piantone, P. (2012), THERMODDEM a database devoted to waste minerals, BRGM, Orléans, France. http://thermoddem.brgm.fr Campolongo, F., Cariboni, J. and Saltelli, A. (2007), An effective screening design for sensitivity analysis of large models, Environmental Modelling & Software 22(10): 1509-1518. Jacques, D. and Šimůnek, J. (2010), Notes on HP1 - a software package for simulating variably-saturated water flow, heat transport, solute transport and biogeochemistry in porous media, HP1 Version 2.2 SCK•CEN-BLG-1068, Waste & Disposal Department, SCK•CEN, Mol, Belgium: 113 p. Morris, M. D. (1991), Factorial Sampling Plans for Preliminary Computational Experiments, Technometrics 33(2): 161-174. Skyllberg, U. (2012), Chemical Speciation of Mercury in Soil and Sediment. Environmental Chemistry and Toxicology of Mercury, John Wiley & Sons, Inc.: 219-258.

In-situ molecular-level elucidation of organofluorine binding sites in a whole peat soil.

PubMed

Longstaffe, James G; Courtier-Murias, Denis; Soong, Ronald; Simpson, Myrna J; Maas, Werner E; Fey, Michael; Hutchins, Howard; Krishnamurthy, Sridevi; Struppe, Jochem; Alaee, Mehran; Kumar, Rajeev; Monette, Martine; Stronks, Henry J; Simpson, André J

2012-10-02

The chemical nature of xenobiotic binding sites in soils is of vital importance to environmental biogeochemistry. Interactions between xenobiotics and the naturally occurring organic constituents of soils are strongly correlated to environmental persistence, bioaccessibility, and ecotoxicity. Nevertheless, because of the complex structural and chemical heterogeneity of soils, studies of these interactions are most commonly performed indirectly, using correlative methods, fractionation, or chemical modification. Here we identify the organic components of an unmodified peat soil where some organofluorine xenobiotic compounds interact using direct molecular-level methods. Using (19)F→(1)H cross-polarization magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy, the (19)F nuclei of organofluorine compounds are used to induce observable transverse magnetization in the (1)H nuclei of organic components of the soil with which they interact after sorption. The observed (19)F→(1)H CP-MAS spectra and dynamics are compared to those produced using model soil organic compounds, lignin and albumin. It is found that lignin-like components can account for the interactions observed in this soil for heptafluoronaphthol (HFNap) while protein structures can account for the interactions observed for perfluorooctanoic acid (PFOA). This study employs novel comprehensive multi-phase (CMP) NMR technology that permits the application of solution-, gel-, and solid-state NMR experiments on intact soil samples in their swollen state.

Surfactant-Induced Changes of Water Flow and Solute Transport in Soils

NASA Astrophysics Data System (ADS)

Kinsey, E. N.; Korte, C.; Peng, Z.; Yu, C.; Powelson, D.; Jacobson, A. R.; Baveye, P. C.; Darnault, C. J. G.

2016-12-01

Surfactants are present in the environment due to agricultural practices such as irrigation with wastewater, biosolid soil amendments, and/or environmental engineering remediation. Furthermore, surfactants occur widely in soils due to the application of pesticides in surfactant solution sprays, or the application of surfactants as soil wetting agents. Surfactants, because they are amphiphilic and impact the surface tension of aqueous solutions and the contact angle between aqueous and solid phases have the potential to influence water flow in porous media and the physicochemical properties of soils. The objective of this study was to assess the impact of surfactant on the soil infiltration process. Four different soils were used in this study: two sandy loam soils (Lewiston and Greenson series) and two loamy sand soils (Sparta and Gilford series). Rainfall was simulated to flow through different columns filled with the four different types of soil and effluent samples were collected at the end of each column. Each type of soil had two columns, one with a non-ionic surfactant Aerosol®22 at twice the critical micelle concentration, in the rainfall solution and one without. A conservative tracer, potassium bromide, was added to all rainfalls to monitor the infiltration process in soil. Tracer breakthrough curves were used to characterize flow in soils. Flow rates were also recorded for each soil. The presence of surfactant decreased the flow rate by a significant amount in most soil types. The decrease in flow rate can be attributed to the effects on the soil properties of hydraulic conductivity and soil aggregates. A decrease in pore space from the swelling of the soil particles can decrease the hydraulic conductivity. The properties in surfactants also decrease the surface tension and therefore soil particles are able to be dislodged from soil aggregates and cause potential soil clogging.

Assessment of priority pesticides, degradation products, and pesticide adjuvants in groundwaters and top soils from agricultural areas of the Ebro river basin.

PubMed

Hildebrandt, Alain; Lacorte, Sílvia; Barceló, Damià

2007-02-01

Gas chromatography-mass spectrometry (GC/MS) was employed for the determination of 30 widely used pesticides including various transformation products and alkylphenols in water and agricultural soils with the aim of assessing the impact of these compounds in agricultural soils and the underlying aquifer. The extraction, clean-up, and analytical procedures were optimized for both water and soil samples to provide a highly robust method capable of determining target analytes at the ppb-ppt level with high precision. For water samples, different solid-phase extraction cartridges and conditions were optimized; similarly, pressurized liquid extraction conditions were tested to provide interference-free extracts and high sensitivity. Instrumental LODs of 3-4 pg were obtained. The multi-residue extraction procedures were applied to the analysis of groundwaters and agricultural soils from the Ebro river basin (NE Spain). Most ubiquitous herbicides detected were triazines but some acetanilides and organophosphorus pesticides were also found; the pesticide additive tributylphosphate was found in all water samples. Levels varied between 0.57 and 5.37 microg/L in groundwater, whereas nonylphenol was the sole compound detected in soil. Alkylphenols are used as adjuvants in pesticide formulations and are present in sludges employed as soil fertilizers. Occurrence was found to be similar to other environmental studies.

Assessing antibiotic sorption in soil: a literature review and new case studies on sulfonamides and macrolides

PubMed Central

2014-01-01

The increased use of veterinary antibiotics in modern agriculture for therapeutic uses and growth promotion has raised concern regarding the environmental impacts of antibiotic residues in soil and water. The mobility and transport of antibiotics in the environment depends on their sorption behavior, which is typically predicted by extrapolating from an experimentally determined soil-water distribution coefficient (Kd). Accurate determination of Kd values is important in order to better predict the environmental fate of antibiotics. In this paper, we examine different analytical approaches in assessing Kd of two major classes of veterinary antibiotics (sulfonamides and macrolides) and compare the existing literature data with experimental data obtained in our laboratory. While environmental parameters such as soil pH and organic matter content are the most significant factors that affect the sorption of antibiotics in soil, it is important to consider the concentrations used, the analytical method employed, and the transformations that can occur when determining Kd values. Application of solid phase extraction and liquid chromatography/mass spectrometry can facilitate accurate determination of Kd at environmentally relevant concentrations. Because the bioavailability of antibiotics in soil depends on their sorption behavior, it is important to examine current practices in assessing their mobility in soil. PMID:24438473

Short-time dissolution mechanisms of kaolinitic tropical soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malengreau, N.; Sposito, Garrison

1996-03-01

Previous research on the short-time dissolution behavior of kaolinitic Oxisols suggested pH-dependent kinetics involving ligand-promoted dissolution, metal readsorption, and colloidal dispersion, with soil organic matter conjectured to play a decisive role. A novel combination of spectroscopy, lightscattering, and batch dissolution experiments, conducted at controlled pH and ionic strength over five dissolution periods ranging from 1 to 12 h, was applied to evaluate this mechanism for samples of a representative kaolinitic Oxisol; collected at both forested and cultivated field sites (leading to significant differences in organic matter content and field soil pH). The overall characteristics of the pH-dependent net release kineticsmore » of Al, Fe, and Si by the soil samples, for any dissolution period in the range investigated, were determined by the pH value at which colloid dispersion commenced, which decreased significantly as the soil organic matter content increased. Plots of log(Si/Al released) (or Si/Fe released) vs. -log [H+] ([H+] is proton concentration) were superimposable for all dissolution periods studied, rising to a plateau value above the point of zero net charge of the soils (pH 3.2). Light-scattering and X-ray diffraction data showed conclusively that this plateau represented the release of siliceous colloids containing kaolinite and X-ray amorphous material. X-ray diffraction, UV-visible diffuse reflectance spectroscopy, and electron spin resonance spectroscopy, applied to the soil samples before and after dissolution, and after conventional chemical extractions to remove Al, C, Fe, and Si, showed that kaolinite and iron oxide phases (the latter being highly Al-substituted and present in both coatings and occlusions) were essentially unaltered by dissolution, even at -log [H+] = 2, whereas substantial dissolution loss of soil quartz occurred. Diffuse reflectance spectroscopy gave strong evidence that C in these soils occurs principally in discrete solid phases, not as a reactive coating on mineral surfaces.« less

Evaluation of the toxicity of two soils from Jales Mine (Portugal) using aquatic bioassays.

PubMed

Loureiro, Susana; Ferreira, Abel L G; Soares, Amadeu M V M; Nogueira, António J A

2005-10-01

Soil contamination can be one path for streams and groundwater contamination. As a complement of chemical analysis and total contaminants determination, bioassays can provide information on the bioavailable fraction of chemical compounds, focusing on the retention and habitat function of soils. In this study the evaluation of the toxicity of two soils from the abandoned Jales Mine (Portugal) regarded both functions. The buffer capacity of soils was tested with bioassays carried out using the cladoceran Daphnia magna and the marine bacteria Vibrio fischeri. The habitat function of soils was evaluated with the reproduction bioassay with the collembolan Folsomia candida. The Microtox solid-phase test was performed with V. fischeri using soil as test medium, and soil elutriates were extracted to perform the Microtox basic test, and an immobilization and reproduction bioassay with D. magna. The marine bacteria showed high sensitivity to the soil with low heavy metal content (JNC soil) and to JNC soil elutriates, while the soil with highest heavy metal content (JC soil) or soil elutriates exposure did not cause any toxic effect. In the bioassays with D. magna, organisms showed sensitivity to JNC and also to JC soil elutriates. Both mobilization and reproduction features were inhibited. The bioassay with F. candida did not reflect any influence of the contaminants on their reproduction. Although JNC soil presented lower heavy metal contents, elutriates showed different patterns of contamination when compared to JC soil and elutriates, which indicates different retention and buffer capacities between soils. Results obtained in this study underlined the sensitivity and importance of soil elutriate bioassays with aquatic organisms in the evaluation strategy in soil ERA processes.

Influence of heating on the weight loss and mineral phase in MSWI ash: LOI of incineration ash

NASA Astrophysics Data System (ADS)

Yang, Shuo

2017-04-01

Loss on ignition (LOI) is a very common method for estimating the volatile species in solid sample. Normally, the measurement of LOI can be convenient and accurate, but for municipal solid waste incineration (MSWI) ash, the process may become intricate due to the complexity of the sample. In the incineration ash, there exist various phases, such as mineral, metal, organic and glass. The reaction and transformation of some materials during heating will influence the measurement. 5 incineration ash samples were selected and tested in this study. LOI content was basically measured at high (850°C) and relatively low (440°C) temperatures. The comparison between these two measurements showed a large difference. X-ray diffraction (XRD) and thermal analysis (TG-DTA) were carried out to investigate the mineral changes and weight losses with different ignition temperatures. The mineralogical analysis suggests that the decomposition of hydrate and carbonate phases cannot be neglected for LOI measurement of incineration. A long-time heating under relatively lower temperature (400∼450°C) compared with soil sample measurement (≥500°C) was recommended by this study.

Greenhouse gas emission and groundwater pollution potentials of soils amended with raw and carbonized swine solids

USDA-ARS?s Scientific Manuscript database

The objective of this research is to study the greenhouse gas emission and groundwater pollution potentials of the soils amended with raw swine solids and swine biochars made from different thermochemical conditions. Triplicate sets of small pots were designed: 1) control soil with a 50/50 mixture o...

Dynamics and transformations of radionuclides in soils and ecosystem health

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fellows, Robert J.; Ainsworth, Calvin C.; Driver, Crystal J.

1998-12-01

The chemical behavior of radionuclides can vary widely in soil and sediment environments. Equally important, for a given radionuclide the physico-chemical properties of the solids and aqueous phase can greatly influence a radionuclides behavior. Radionuclides can conceivably occur in soils as soluble-free, inorganic-soluble-complexed, organic-soluble, complexed, adsorbed, precipitated, coprecipitated, or solid structural species. While it is clear that an assessment of a radionuclide?s soil chemistry and potential shifts in speciation will yield a considerable understanding of its behavior in the natural environment, it does not directly translate to bioavailability or its impact on ecosystems health. The soil chemical factors have tomore » be linked to food chain considerations and other ecological parameters that directly tie to an analysis of ecosystem health. In general, the movement of radionuclides from lower to higher trophic levels diminishes with each trophic level in both aqua tic and terrestrial systems. In some cases, transfer is limited because of low absorption/assimilation by successive trophic organisms (Pu, U); for other radionuclides (Tc, H) assimilation may be high but rapid metabolic turnover and low retention greatly reduce tissue concentrations available to predator species. Still others are chemical analogs of essential elements whose concentrations are maintained under strict metabolic control in tissues (Cs) or are stored in tissues seldom consumed by other organisms (Sr storage in exoskeleton, shells, and bone). Therefore, the organisms that receive the greatest ingestion exposures are those in lower trophic positions or are in higher trophic levels but within simple, short food chains. Food source, behavior, and habitat influence the accumulation of radionuclides in animals.« less

Hydration Phase Diagram of Clay Particles from Molecular Simulations.

PubMed

Honorio, Tulio; Brochard, Laurent; Vandamme, Matthieu

2017-11-07

Adsorption plays a fundamental role in the behavior of clays. Because of the confinement between solid clay layers on the nanoscale, adsorbed water is structured in layers, which can occupy a specific volume. The transition between these states is intimately related to key features of clay thermo-hydro-mechanical behavior. In this article, we consider the hydration states of clays as phases and the transition between these states as phase changes. The thermodynamic formulation supporting this idea is presented. Then, the results from grand canonical Monte Carlo simulations of sodium montmorillonite are used to derive hydration phase diagrams. The stability analysis presented here explains the coexistence of different hydration states at clay particle scale and improves our understanding of the irreversibilities of clay thermo-hydro-mechanical behavior. Our results provide insights into the mechanics of the elementary constituents of clays, which is crucial for a better understanding of the macroscopic behavior of clay-rich rocks and soils.

Revealing the micromechanisms behind semi-solid metal deformation with time-resolved X-ray tomography.

PubMed

Kareh, K M; Lee, P D; Atwood, R C; Connolley, T; Gourlay, C M

2014-07-18

The behaviour of granular solid-liquid mixtures is key when deforming a wide range of materials from cornstarch slurries to soils, rock and magma flows. Here we demonstrate that treating semi-solid alloys as a granular fluid is critical to understanding flow behaviour and defect formation during casting. Using synchrotron X-ray tomography, we directly measure the discrete grain response during uniaxial compression. We show that the stress-strain response at 64-93% solid is due to the shear-induced dilation of discrete rearranging grains. This leads to the counter-intuitive result that, in unfed samples, compression can open internal pores and draw the free surface into the liquid, resulting in cracking. A soil mechanics approach shows that, irrespective of initial solid fraction, the solid packing density moves towards a constant value during deformation, consistent with the existence of a critical state in mushy alloys analogous to soils.

78 FR 48158 - Intent To Grant an Exclusive Patent License

Federal Register 2010, 2011, 2012, 2013, 2014

2013-08-07

... HYDROCARBONS AND ETHERS IN SUBSURFACE SOIL BY INTRODUCTION OF A SOLID OXYGEN SOURCE BY HYDRAULIC FRACTURING... IN SUBSURFACE SOIL BY INTRODUCTION OF A SOLID OXYGEN SOURCE BY HYDRAULIC FRACTURING, filed as U.S...

Distribution and biogeochemical controls on net methylmercury production in Penobscot River marshes and sediment.

PubMed

Gilmour, Cynthia; Bell, James Tyler; Soren, Ally Bullock; Riedel, Georgia; Riedel, Gerhardt; Kopec, A Dianne; Bodaly, R A

2018-06-01

The distribution of mercury and methylmercury (MeHg) in sediment, mudflats, and marsh soils of the Hg-contaminated tidal Penobscot River was investigated, along with biogeochemical controls on production. Average total Hg in surface samples (0-3 cm) ranged from 100 to 1200 ng/g; average MeHg ranged from 5 to 50 ng/g. MeHg was usually highest at or near the surface except in highly mobile mudflats. Although total Hg concentrations in the Penobscot are elevated, it is the accumulation of MeHg that stands out in comparison to other ecosystems. Surface soils in the large Mendall Marsh, about 17 km downstream from the contamination source, contained particularly high %MeHg (averaging 8%). In Mendall marsh soil porewaters, MeHg often accounted for more than half of total Hg. Salt marshes are areas of particular concern in the Penobscot River, for they are depositional environments for a Hg-contaminated mobile pool of river sediment, hot spots for net MeHg production, and sources of risk to marsh animals. We hypothesized that exceptionally low mercury partitioning between the solid and aqueous phases (with log K d averaging ~4.5) drives high MeHg in Penobscot marshes. The co-occurrence of iron and sulfide in filtered soil porewaters, sometimes both above 100 μM, suggests the presence of nanoparticulate and/or colloidal metal sulfides. These colloids may be stabilized by high concentrations of aromatic and potentially sulfurized dissolved organic matter (DOM) in marsh soils. Thus, Hg in Penobscot marsh soils appears to be in a highly available for microbial methylation through the formation of DOM-associated HgS complexes. Additionally, low partitioning of MeHg to marsh soils suggests high MeHg bioavailability to animals. Overall, drivers of high MeHg in Penobscot marshes include elevated Hg in soils, low partitioning of Hg to solids, high Hg bioavailability for methylation, rapidly shifting redox conditions in surface marsh soils, and high rates of microbial activity. Copyright © 2018 Elsevier B.V. All rights reserved.

Environmental risk assessment of the use of different organic wastes as soil amendments

NASA Astrophysics Data System (ADS)

Alvarenga, Paula; Palma, Patrícia; Mourinha, Clarisse; Farto, Márcia; Cunha-Queda, Ana Cristina; Natal-da-Luz, Tiago; Sousa, José Paulo

2013-04-01

The use of organic wastes in agriculture is considered a way of maintaining or restoring the quality of soils, enlarging the slow cycling soil organic carbon pool. However, a wide variety of undesired substances, such as potentially trace elements and organic contaminants, can have adverse effects on the environment. That fact was highlighted by the Proposal for a Soil Framework Directive, which recognized that "soil degradation or soil improvements have a major impact on other areas, (…) such as surface waters and groundwater, human health, climate change, protection of nature and biodiversity, and food safety". Taking that into account, the research project "ResOrgRisk" aims to assess the environmental risk involved in the use of different organic wastes as soil amendments, evidencing their benefits and constraints, and defining the most suitable tests to reach such assessment. The organic wastes selected for this purpose were: sewage sludge, limed, not limed, and co-composted with agricultural wastes, agro-industrial sludge, mixed municipal solid waste compost, compost produced from organic farming residues, and pig slurry digestate. Whereas threshold values for heavy metals in sludge used for agriculture have been set by the European Commission, actually there is no definitive European legislation for organic contaminants. Guide values for some organic contaminants (e.g. polychlorinated biphenyls - PCBs, and polycyclic aromatic hydrocarbons - PAHs) have been adopted at national level by many European countries, such as Portugal. These values should be taken into account when assessing the risk involved in the use of organic wastes as soil amendments. However, chemical analysis of organic waste often gives scarce information because it does not include possible interactions between chemicals. Furthermore, an exhaustive identification and quantification of all substances is impractical. In this study, ecotoxicological tests (comprising solid and aquatic phases) were performed to obtain an integrated assessment on the effects of all contaminants from each organic waste, as a whole, to terrestrial systems. The results for the chemical and ecotoxicological characterization of the organic wastes selected in this study will be discussed, emphasizing the potential benefits and the risks of their use as soil amendments.

The use of MP-AES for determination of plant available P in soil by DL method and distribution of soils into P status classes by DL, AL and Mehlich 3 methods.

NASA Astrophysics Data System (ADS)

Toomsoo, Avo; Jürgens, Meit; Kõlli, Raimo; Künnapas, Allan; Albre, Imbi; Tõnutare, Tõnu; Rodima, Ako

2017-04-01

Only small percentage of soil total phosphorus is easily exchangeable between solid and solution phase. Plants are able to assimilate P from environment only in the form of orthophosphate ions (H2PO4- and HPO42-) from soil solution. Deficit of P in soil solution prevents plant normal growth and decreases yield quantity and quality. The excess of P in soil solution causes the pollution of environment and eutrophication of water bodies. Therefore it is important to give to the plant producers the correct fertilization recommendations. Lot of analytical methods are developed for the determination of plant available P in soils. In the Baltic Sea region seven different soils' P analysis methods in use. Each method has its own gradation and often there is more than one gradation for the same method depending from agroecological conditions. For agricultural soils in Estonia there are soil P status gradations according to Mehlich 3, DL and AL methods. Phosphate content in soil can be determined by molybdate method Vis-spectrometrically. Very often for analysis of soils' P content also ICP-OES, ICP-MS and also MP-AES instrumental methods are used The aim of our work was to investigate the possibility of using MP-AES for determination of plant available P in soil by DL method and also to compare how the analysed soils are distributed to M3, AL and DL fertilizer requirement groups according to the P content.

Analysis of some chlorophenoxy acids and carbamate herbicides in water and soil as amide derivatives using gas chromatography-mass spectrometry.

PubMed

Salem, A A

2007-03-01

A newly developed method for determining three phenoxy acids and one carbamate herbicide in water and soil samples using gas chromatography with mass spectrometric detection is developed. Phenoxy acids are derivatized through a condensation reaction with a suitable aromatic amine. 1,1-Carbonyldiimidazole is used as a condensation reagent. Derivatization conditions are optimized with respect to the amount of analyte, amine, solvent, and derivatization reagent. The optimum derivatization yield is accomplished in acetonitrile. 4-Methoxy aniline is used as a derivatizing agent. Obtained derivatives are stable indefinitely. Enhancement in sensitivity is achieved by using the single-ion monitoring mass spectrometric mode. The effectiveness of the developed method is tested by determining investigated compounds in water and soil samples. Analytes are concentrated from water samples using liquid-phase extraction and solid-phase extraction. Soil samples are extracted using methanol. Detection limits of 1.00, 50.00, 100.00, and 1.00 ng/mL are obtained for 2-(1-methylethoxy)phenyl methylcarbamate (Baygon), 2-(3-chlorophenoxy)-propionic acid (Cloprop), 2,4,5-trichlorophenoxyacetic acid, and 4-(2,4-dichlorophenoxy)butyric acid, respectively. LPE for spiked water samples yields recoveries in the range of 60.6-95.7%, with relative standard deviation (RSD) values of 1.07-7.85% using single component calibration curves. Recoveries of 44.8-275.5%, with RSD values ranging from 1.43% to 8.61% were obtained using a mixed component calibration curves. SPE from water samples and soil samples showed low recoveries. The reason is attributed to the weak sorption capabilities of soil and Al(2)O(3).

Evaluation of engineering properties for the use of leached brown coal ash in soil covers.

PubMed

Mudd, Gavin M; Chakrabarti, Srijib; Kodikara, Jayantha

2007-01-31

The need to engineer cover systems for the successful rehabilitation or remediation of a wide variety of solid wastes is increasing. Some common applications include landfills, hazardous waste repositories, or mine tailings dams and waste rock/overburden dumps. The brown coal industry of the Latrobe Valley region of Victoria, Australia, produces significant quantities of coal ash and overburden annually. There are some site-specific acid mine drainage (AMD) issues associated with overburden material. This needs to be addressed both during the operational phase of a project and during rehabilitation. An innovative approach was taken to investigate the potential to use leached brown coal ash in engineered soil covers on this overburden dump. The basis for this is two-fold: first, the ash has favourable physical characteristics for use in cover systems (such as high storage capacity/porosity, moderately low permeability, and an ability to act as a capillary break layer generating minimal leachate or seepage); and second, the leachate from the ash is mildly alkaline (which can help to mitigate and reduce the risk of AMD). This paper will review the engineering issues involved in using leached brown coal ash in designing soil covers for potentially acid-forming overburden dumps. It presents the results of laboratory work investigating the technical feasibility of using leached brown coal ash in engineered solid waste cover systems.

Effect of short-chain organic acids on the enhanced desorption of phenanthrene by rhamnolipid biosurfactant in soil-water environment.

PubMed

An, Chun-jiang; Huang, Guo-he; Wei, Jia; Yu, Hui

2011-11-01

This study investigated the effect of short-chain organic acids on biosurfactant-enhanced mobilization of phenanthrene in soil-water system. The desorption characteristics of phenanthrene by soils were assessed in the presence of rhamnolipid and four SCOAs, including acetic acid, oxalic acid, tartaric acid and citric acid. The tests with rhamnolipid and different organic acids could attain the higher desorption of phenanthrene compared to those with only rhamnolipid. Among the different combinations, the series with rhamnolipid and citric acid exhibited more significant effect on the desorption performance. The removal of phenanthrene using rhamnolipid and SCOAs gradually increased as the SCOA concentration increased up to a concentration of 300 mmol/L. The effects of pH, soil dissolved organic matter and ionic strength were further evaluated in the presence of both biosurfactant and SCOAs. The results showed that the extent of phenanthrene desorption was more significant at pH 6 and 9. Desorption of phenanthrene was relatively lower in the DOM-removed soils with the addition of biosurfactant and SCOAs. The presence of more salt ions made phenanthrene more persistent on the solid phase and adversely affected its desorption from contaminated soil. The results from this study may have important implications for soil washing technologies used to treat PAH-contaminated soil and groundwater. Copyright © 2011 Elsevier Ltd. All rights reserved.

Mixed-mode sorption of hydroxylated atrazine degradation products to sell: A mechanism for bound residue

USGS Publications Warehouse

Lerch, R.N.; Thurman, E.M.; Kruger, E.L.

1997-01-01

This study tested the hypothesis that sorption of hydroxylated atrazine degradation products (HADPs: hydroxyatrazine, HA; deethylhydroxyatrazine, DEHA; and deisopropylhydroxyatrazine, DIHA) to soils occurs by mixed-mode binding resulting from two simultaneous mechanisms: (1) cation exchange and (2) hydrophobic interaction. The objective was to use liquid chromatography and soil extraction experiments to show that mixed-mode binding is the mechanism controlling HADP sorption to soils and is also a mechanism for bound residue. Overall, HADP binding to solid-phase extraction (SPE) sorbents occurred in the order: cation exchange >> octadecyl (C18) >> cyanopropyl. Binding to cation exchange SPE and to a high-performance liquid chromatograph octyl (C8) column showed evidence for mixed-mode binding. Comparison of soil extracted by 0.5 M KH2P04, pH 7.5, or 25% aqueous CH3CN showed that, for HA and DIHA, cation exchange was a more important binding mechanism to soils than hydrophobic interaction. Based on differences between several extractants, the extent of HADP mixed-mode binding to soil occurred in the following order: HA > DIHA > DEHA. Mixed-mode extraction recovered 42.8% of bound atrazine residues from aged soil, and 88% of this fraction was identified as HADPs. Thus, a significant portion of bound atrazine residues in soils is sorbed by the mixed-mode binding mechanisms.

The bioavailability of chemicals in soil for earthworms

USGS Publications Warehouse

Lanno, R.; Wells, J.; Conder, Jason M.; Bradham, K.; Basta, N.

2004-01-01

The bioavailability of chemicals to earthworms can be modified dramatically by soil physical/chemical characteristics, yet expressing exposure as total chemical concentrations does not address this problem. In order to understand the effects of modifying factors on bioavailability, one must measure and express chemical bioavailability to earthworms in a consistent, logical manner. This can be accomplished by direct biological measures of bioavailability (e.g., bioaccumulation, critical body residues), indirect biological measures of bioavailability (e.g., biomarkers, reproduction), or indirect chemical measures of bioavailability (e.g., chemical or solid-phase extracts of soil). If indirect chemical measures of bioavailability are to be used, they must be correlated with some biological response. Bioavailability can be incorporated into ecological risk assessment during risk analysis, primarily in the estimation of exposure. However, in order to be used in the site-specific ecological risk assessment of chemicals, effects concentrations must be developed from laboratory toxicity tests based on exposure estimates utilizing techniques that measure the bioavailable fraction of chemicals in soil, not total chemical concentrations. ?? 2003 Elsevier Inc. All rights reserved.

Carbon and nitrogen accumulation and fluxes on Landscape Evolution Observatory (LEO) slopes

NASA Astrophysics Data System (ADS)

Dontsova, K.; Volk, M.; Webb, C.; Hunt, E.; Tfaily, M. M.; Van Haren, J. L. M.; Sengupta, A.; Chorover, J.; Troch, P.; Ruiz, J.

2017-12-01

Carbon accumulation on the landscapes in organic and inorganic forms is an important sink of CO2 from the atmosphere. Formation and preservation of organic compounds is accompanied by N fixation from the atmosphere and cycling in the soil. Model slopes of Landscape Evolution Observatory present unique opportunity to examine carbon and nitrogen buildup on the landscapes during soil formation processes, such as weathering of primary minerals and microbial activity, due to low original levels of C and N, tight control over environmental conditions, and high spatial and temporal density of measurements. This presents results of inorganic and organic C and N measurements in the cores collected in LEO slopes after several years of exposure to the rainfall, as well as soil solution measurements collected through 496 samplers on each of three model slopes and in seepage. We observed significant spatially distributed accumulation of both C (organic and inorganic) and N in soil profiles. We also observed differences in the composition of organic compounds in the solid and solution phases depending on location on the slope indicating formation of heterogeneity as soils develop. This works indicates potential of physical models to help understand accumulation and fluxes of C and N on natural landscapes.

Preconcentration of Sn (II) using the methylene blue on the activated carbon and its determination by spectrophotometry method.

PubMed

Khodadoust, Saeid; Cham Kouri, Narges

2014-04-05

A simple and accurate spectrophotometric method for determination of trace amounts of Sn (II) ion in soil sample was developed by using the methylene blue (MB) in the presence of activated carbon (AC) as the adsorbent Solid Phase Extraction (SPE) of Sn (II) and then determined by UV-Vis. The Beer's law is obeyed over the concentration range of 1-80ngmL(-1) of Sn (II) with the detection limits of 0.34ngmL(-1). The influence of type and volume of eluent, concentration of MB, pH, and amount of AC on sensitivity of spectrophotometric method were optimized. The method has been successfully applied for Sn (II) ion determination in soil sample. Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of diacylhydrazines-type insect growth regulator JS-118 residues in cabbage and soil by high performance liquid chromatography with DAD detection.

PubMed

Hu, J-Y; Deng, Z-B; Qin, D-M

2009-12-01

JS-118 is a diacylhydrazines-type insect growth regulator used extensively in China now. An analytical method for residues determination of JS-118 in cabbage and soil samples by high performance liquid chromatography with DAD detection was established and optimized. Primary secondary amine solid phase extraction cartridge was used for sample preparation. Mean recoveries for the analyte ranged from 96.6% to 107.0% with CV value less than 4.7%. The limit of quantification is 0.01 mg/kg. Direct confirmation of JS-118 residues in samples was realized by high performance liquid chromatography-mass spectrometry. The proposed method is simple, rapid and reliable to perform and could be utilized for monitoring of pesticides residues.

Solid phase evolution in the Biosphere 2 hillslope experiment as predicted by modeling of hydrologic and geochemical fluxes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dontsova, K.; Steefel, C.I.; Desilets, S.

2009-07-15

A reactive transport geochemical modeling study was conducted to help predict the mineral transformations occurring over a ten year time-scale that are expected to impact soil hydraulic properties in the Biosphere 2 (B2) synthetic hillslope experiment. The modeling sought to predict the rate and extent of weathering of a granular basalt (selected for hillslope construction) as a function of climatic drivers, and to assess the feedback effects of such weathering processes on the hydraulic properties of the hillslope. Flow vectors were imported from HYDRUS into a reactive transport code, CrunchFlow2007, which was then used to model mineral weathering coupled tomore » reactive solute transport. Associated particle size evolution was translated into changes in saturated hydraulic conductivity using Rosetta software. We found that flow characteristics, including velocity and saturation, strongly influenced the predicted extent of incongruent mineral weathering and neo-phase precipitation on the hillslope. Results were also highly sensitive to specific surface areas of the soil media, consistent with surface reaction controls on dissolution. Effects of fluid flow on weathering resulted in significant differences in the prediction of soil particle size distributions, which should feedback to alter hillslope hydraulic conductivities.« less

Processes affecting the remediation of chromium-contaminated sites.

PubMed

Palmer, C D; Wittbrodt, P R

1991-05-01

The remediation of chromium-contaminated sites requires knowledge of the processes that control the migration and transformation of chromium. Advection, dispersion, and diffusion are physical processes affecting the rate at which contaminants can migrate in the subsurface. Heterogeneity is an important factor that affects the contribution of each of these mechanisms to the migration of chromium-laden waters. Redox reactions, chemical speciation, adsorption/desorption phenomena, and precipitation/dissolution reactions control the transformation and mobility of chromium. The reduction of CrVI to CrIII can occur in the presence of ferrous iron in solution or in mineral phases, reduced sulfur compounds, or soil organic matter. At neutral to alkaline pH, the CrIII precipitates as amorphous hydroxides or forms complexes with organic matter. CrIII is oxidized by manganese dioxide, a common mineral found in many soils. Solid-phase precipitates of hexavalent chromium such as barium chromate can serve either as sources or sinks for CrVI. Adsorption of CrVI in soils increases with decreasing chromium concentration, making it more difficult to remove the chromium as the concentration decreases during pump-and-treat remediation. Knowledge of these chemical and physical processes is important in developing and selecting effective, cost-efficient remediation designs for chromium-contaminated sites.

Release and transport of mobile organic matter and biocolloids: A combined physicochemical and microbiological study

NASA Astrophysics Data System (ADS)

Reichel, Katharina; Schaefer, Sabine; Babin, Doreen; Smalla, Konny; Totsche, Kai Uwe

2016-04-01

Biogeochemical interfaces within the aggregate system of soils are "hot spots" of microbial activity and turnover of organic matter. We explore turnover, release and transport of mobile organic matter (MOM), micro-organisms (bio-colloids) and organo-mineral associations using a novel experimental approach employing two-layer columns experiment with matured soil under unsaturated flow conditions. The top layer was spiked with phenanthrene as a tracer for studying the decomposer communities involved in the decomposition of aromatic compounds that derive from lignin in natural systems. Columns were irrigated with artificial rain water with several flow interrupts of different durations. Physicochemical and chemical parameters as well as the microbial community composition were analysed in effluent samples and in soil slices. Release of MOM from the columns was in general controlled by non-equilibrium. Export of total and dissolved organic matter differed significantly in response to the flow interrupts. Effluent comprised organic and organo-mineral components as well as vital competent cells. By molecular biological methods we were even able to show that bacterial consortia exported are rather divers. Depth distribution of the bacterial communities associated with the immobile solid phase indicated high similarities in bacterial communities of the different depth layers and treatments. According to phenanthrene high affinity to the immobile phases, only a small fraction was subject to downstream transport with a strong decrease of the amount residing at the solid phase Our experiments directly prove that intact and competent microorganisms and even communities can be transported under unsaturated flow conditions. Moreover, we found that the dominant carbon source will impact not only the activity of specific microbial taxa but also their mobilization and transport. While total contribution of microbial organism to the mobile organic matter pool seems to be small, the fact that microbes will be mobilized and passively transported to downstream compartments helps to understand the processes that result in the inhabitation of pristine surfaces, thereby resulting in the establishment biogeochemical interfaces and initiation of aggregation in downstream compartments in the vadose zone.

Magnetic separation of general solid particles realised by a permanent magnet

PubMed Central

Hisayoshi, K.; Uyeda, C.; Terada, K.

2016-01-01

Most existing solids are categorised as diamagnetic or weak paramagnetic materials. The possibility of magnetic motion has not been intensively considered for these materials. Here, we demonstrate for the first time that ensembles of heterogeneous particles (diamagnetic bismuth, diamond and graphite particles, as well as two paramagnetic olivines) can be dynamically separated into five fractions by the low field produced by neodymium (NdFeB) magnets during short-duration microgravity (μg). This result is in contrast to the generally accepted notion that ordinary solid materials are magnetically inert. The materials of the separated particles are identified by their magnetic susceptibility (χ), which is determined from the translating velocity. The potential of this approach as an analytical technique is comparable to that of chromatography separation because the extraction of new solid phases from a heterogeneous grain ensemble will lead to important discoveries about inorganic materials. The method is applicable for the separation of the precious samples such as lunar soils and/or the Hayabusa particles recovered from the asteroids, because even micron-order grains can be thoroughly separated without sample-loss. PMID:27929081

Magnetic separation of general solid particles realised by a permanent magnet

NASA Astrophysics Data System (ADS)

Hisayoshi, K.; Uyeda, C.; Terada, K.

2016-12-01

Most existing solids are categorised as diamagnetic or weak paramagnetic materials. The possibility of magnetic motion has not been intensively considered for these materials. Here, we demonstrate for the first time that ensembles of heterogeneous particles (diamagnetic bismuth, diamond and graphite particles, as well as two paramagnetic olivines) can be dynamically separated into five fractions by the low field produced by neodymium (NdFeB) magnets during short-duration microgravity (μg). This result is in contrast to the generally accepted notion that ordinary solid materials are magnetically inert. The materials of the separated particles are identified by their magnetic susceptibility (χ), which is determined from the translating velocity. The potential of this approach as an analytical technique is comparable to that of chromatography separation because the extraction of new solid phases from a heterogeneous grain ensemble will lead to important discoveries about inorganic materials. The method is applicable for the separation of the precious samples such as lunar soils and/or the Hayabusa particles recovered from the asteroids, because even micron-order grains can be thoroughly separated without sample-loss.

Magnetic separation of general solid particles realised by a permanent magnet.

PubMed

Hisayoshi, K; Uyeda, C; Terada, K

2016-12-08

Most existing solids are categorised as diamagnetic or weak paramagnetic materials. The possibility of magnetic motion has not been intensively considered for these materials. Here, we demonstrate for the first time that ensembles of heterogeneous particles (diamagnetic bismuth, diamond and graphite particles, as well as two paramagnetic olivines) can be dynamically separated into five fractions by the low field produced by neodymium (NdFeB) magnets during short-duration microgravity (μg). This result is in contrast to the generally accepted notion that ordinary solid materials are magnetically inert. The materials of the separated particles are identified by their magnetic susceptibility (χ), which is determined from the translating velocity. The potential of this approach as an analytical technique is comparable to that of chromatography separation because the extraction of new solid phases from a heterogeneous grain ensemble will lead to important discoveries about inorganic materials. The method is applicable for the separation of the precious samples such as lunar soils and/or the Hayabusa particles recovered from the asteroids, because even micron-order grains can be thoroughly separated without sample-loss.

Organic matter and salinity modify cadmium soil (phyto)availability.

PubMed

Filipović, Lana; Romić, Marija; Romić, Davor; Filipović, Vilim; Ondrašek, Gabrijel

2018-01-01

Although Cd availability depends on its total concentration in soil, it is ultimately defined by the processes which control its mobility, transformations and soil solution speciation. Cd mobility between different soil fractions can be significantly affected by certain pedovariables such as soil organic matter (SOM; over formation of metal-organic complexes) and/or soil salinity (over formation of metal-inorganic complexes). Phytoavailable Cd fraction may be described as the proportion of the available Cd in soil which is actually accessible by roots and available for plant uptake. Therefore, in a greenhouse pot experiment Cd availability was observed in the rhizosphere of faba bean exposed to different levels of SOM, NaCl salinity (50 and 100mM) and Cd contamination (5 and 10mgkg -1 ). Cd availability in soil does not linearly follow its total concentration. Still, increasing soil Cd concentration may lead to increased Cd phytoavailability if the proportion of Cd 2+ pool in soil solution is enhanced. Reduced Cd (phyto)availability by raised SOM was found, along with increased proportion of Cd-DOC complexes in soil solution. Data suggest decreased Cd soil (phyto)availability with the application of salts. NaCl salinity affected Cd speciation in soil solution by promoting the formation of CdCl n 2-n complexes. Results possibly suggest that increased Cd mobility in soil does not result in its increased availability if soil adsorption capacity for Cd has not been exceeded. Accordingly, chloro-complex possibly operated just as a Cd carrier between different soil fractions and resulted only in transfer between solid phases and not in increased (phyto)availability. Copyright © 2017 Elsevier Inc. All rights reserved.

Moisture stable Ni-Zn MOF/g-C3N4 nanoflowers: A highly efficient adsorbent for solid-phase microextraction of PAHs.

PubMed

Zhang, Ning; Huang, Chuanhui; Tong, Ping; Feng, Zunmei; Wu, Xiaoping; Zhang, Lan

2018-06-29

Volatile polycyclic aromatic hydrocarbons (PAHs) in water and soil are associated with status in the human body. Development of simple, efficient detection method is challenging due to the coating could be attacked by the abundance of water in the direct-immersion solid-phase microextraction. The stability of coating is essential to the analysis results. In this paper, a stable Ni-Zn MOF/g-C 3 N 4 (MG NFs) nanoflowers with cavity traps structure was firstly reported and acted as solid-phase microextraction (SPME) adsorbent for PAHs. Markedly enhanced moisture and acid stability of the MG NFs was obtained through the doping the hydrophobic graphitic carbon nitride (g-C 3 N 4 ) and metal ions into metal organic frameworks (MOFs). The aperture environment and ambient environment of MG NFs were changed by the doping of the Ni and the g-C 3 N 4, respectively. The moisture and acid stability of MG NFs were prominently increased under the dual protection. Compared to commonly used commercial coatings, the MG NFs own large surface area, unique nanoflowers structure and numerous open metal sites on the nanosheets, which demonstrated significant extraction superiority for PAHs. The MG NFs coated fiber was used for the SPME preconcentration of PAHs and couped with GC-MS for detecting PAHs. It presented low detection limits (0.1-3.0 ng L -1 ), wide linearity (0.3-5000.0 ng L -1 ) and good linearity (the correlation coefficient >0.9951). The inter-day and intra-day relative standard deviation (RSD) (n = 3) for three replicate extractions using one fiber was 3.8%-9.1%, and 3.5%-9.2%, respectively. The fiber-to-fiber reproducibility (n = 3) was 4.2-11.8%. The coupling method was successfully applied in the analysis of real water and soil samples with satisfactory recoveries of 82.9-109.2%, 84.2-106.4%, and the corresponding RSDs were 2.4-11.3%, 3.6-10.8%, respectively. The results indicated the effectiveness of NG NFs coated fiber in further practical application. Copyright © 2018 Elsevier B.V. All rights reserved.

Sea Level Rise Induced Arsenic Release from Historically Contaminated Coastal Soils.

PubMed

LeMonte, Joshua J; Stuckey, Jason W; Sanchez, Joshua Z; Tappero, Ryan; Rinklebe, Jörg; Sparks, Donald L

2017-06-06

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions. We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.

Can ligand addition to soil enhance Cd phytoextraction? A mechanistic model study.

PubMed

Lin, Zhongbing; Schneider, André; Nguyen, Christophe; Sterckeman, Thibault

2014-11-01

Phytoextraction is a potential method for cleaning Cd-polluted soils. Ligand addition to soil is expected to enhance Cd phytoextraction. However, experimental results show that this addition has contradictory effects on plant Cd uptake. A mechanistic model simulating the reaction kinetics (adsorption on solid phase, complexation in solution), transport (convection, diffusion) and root absorption (symplastic, apoplastic) of Cd and its complexes in soil was developed. This was used to calculate plant Cd uptake with and without ligand addition in a great number of combinations of soil, ligand and plant characteristics, varying the parameters within defined domains. Ligand addition generally strongly reduced hydrated Cd (Cd(2+)) concentration in soil solution through Cd complexation. Dissociation of Cd complex ([Formula: see text]) could not compensate for this reduction, which greatly lowered Cd(2+) symplastic uptake by roots. The apoplastic uptake of [Formula: see text] was not sufficient to compensate for the decrease in symplastic uptake. This explained why in the majority of the cases, ligand addition resulted in the reduction of the simulated Cd phytoextraction. A few results showed an enhanced phytoextraction in very particular conditions (strong plant transpiration with high apoplastic Cd uptake capacity), but this enhancement was very limited, making chelant-enhanced phytoextraction poorly efficient for Cd.

Sea Level Rise Induced Arsenic Release from Historically Contaminated Coastal Soils

DOE PAGES

LeMonte, Joshua J.; Stuckey, Jason W.; Sanchez, Joshua Z.; ...

2017-05-04

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions.more » We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Here, our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.« less

Sea Level Rise Induced Arsenic Release from Historically Contaminated Coastal Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

LeMonte, Joshua J.; Stuckey, Jason W.; Sanchez, Joshua Z.

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions.more » We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Here, our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.« less

The effect of different treatment technologies on the fate of antibiotic resistance genes and class 1 integrons after the application of residual municipal wastewater solids to soil

USDA-ARS?s Scientific Manuscript database

Land-application of residual wastewater solids is an important environmental source of antibiotic resistance genes (ARGs). Treatment technologies exist that can reduce ARG levels in residual solids prior to land-application, but the effect of these technologies on ARG levels in soil following land-a...

Sorption and phase distribution of ethanol and butanol blended gasoline vapours in the vadose zone after release.

PubMed

Ugwoha, Ejikeme; Andresen, John M

2014-03-01

The sorption and phase distribution of 20% ethanol and butanol blended gasoline (E20 and B20) vapours have been examined in soils with varying soil organic matter (SOM) and water contents via laboratory microcosm experiments. The presence of 20% alcohol reduced the sorption of gasoline compounds by soil as well as the mass distribution of the compounds to soil solids. This effect was greater for ethanol than butanol. Compared with the sorption coefficient (Kd) of unblended gasoline compounds, the Kd of E20 gasoline compounds decreased by 54% for pentane, 54% for methylcyclopentane (MCP) and 63% for benzene, while the Kd of B20 gasoline compounds decreased by 39% for pentane, 38% for MCP and 49% for benzene. The retardation factor (R) of E20 gasoline compounds decreased by 53% for pentane, 53% for MCP and 48% for benzene, while the R of B20 gasoline compounds decreased by 39% for pentane, 37% for MCP and 38% for benzene. For all SOM and water contents tested, the Kd and R of all gasoline compounds were in the order of unblended gasoline > B20 > E20, indicating that the use of high ethanol volume in gasoline to combat climate change could put the groundwater at greater risk of contamination. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Anaerobic digestion of municipal solid waste: Utility of process residues as a soil amendment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rivard, C.J.; Nagle, N.J.; Kay, B.D.

1995-12-31

Tuna processing wastes (sludges high in fat, oil, and grease [FOG]) and municipal solid waste (MSW) generated on Tutuila Island, American Samoa, represent an ongoing disposal challenge. The biological conversion of the organic fraction of these wastes to useful products, including methane and fertilizer-grade residue, through anaerobic high-solids digestion is currently in scale-up development. The suitability of the anaerobic digestion residues as a soil amendment was evaluated through extensive chemical analysis and greenhouse studies using corn as an indicator crop. Additionally, native Samoan soil was used to evaluate the specific application rates for the compost. Experiments established that anaerobic residuesmore » increase crop yields in direct proportion to increases in the application rate. Additionally, nutrient saturation was not demonstrated within the range of application rates evaluated for the Samoan soil. Beyond nutrient supplementation, organic residue amendment to Samoan soil imparts enhanced water and nutrient-binding capacities.« less

Utilization of phosphorus loaded alkaline residue to immobilize lead in a shooting range soil.

PubMed

Yan, Yubo; Qi, Fangjie; Seshadri, Balaji; Xu, Yilu; Hou, Jiexi; Ok, Yong Sik; Dong, Xiaoli; Li, Qiao; Sun, Xiuyun; Wang, Lianjun; Bolan, Nanthi

2016-11-01

The alkaline residue generated from the production of soda ash using the ammonia-soda method has been successfully used in removing phosphorus (P) from aqueous solution. But the accumulation of P-containing solid after P removal is an undesirable menace to the environment. To achieve the goal of recycling, this study explored the feasibility of reusing the P loaded alkaline residue as an amendment for immobilization of lead (Pb) in a shooting range soil. The main crystalline phase and micromorphology of amendments were determined using X-ray diffraction (XRD) and scanning electron microscopy-electron dispersion spectroscopy (SEM-EDS) methods. The toxicity characteristic leaching procedure (TCLP), sequential extraction procedure, and physiologically based extraction test (PBET) were employed to evaluate the effectiveness of Pb immobilization in soil after 45 d incubation. Treatment with P loaded alkaline residue was significantly effective in reducing the TCLP and PBET extractable Pb concentrations in contrast to the untreated soil. Moreover, a positive change in the distribution of Pb fractions was observed in the treated soil, i.e., more than 60% of soil-Pb was transformed to the residual fraction compared to the original soil. On the other hand, P loaded amendments also resulted in a drastic reduction in phytoavailable Pb to the winter wheat and a mild release of P as a nutrient in treated soil, which also confirmed the improvement of soil quality. Copyright © 2016 Elsevier Ltd. All rights reserved.

Revealing the micromechanisms behind semi-solid metal deformation with time-resolved X-ray tomography

PubMed Central

Kareh, K. M.; Lee, P. D.; Atwood, R. C.; Connolley, T.; Gourlay, C. M.

2014-01-01

The behaviour of granular solid–liquid mixtures is key when deforming a wide range of materials from cornstarch slurries to soils, rock and magma flows. Here we demonstrate that treating semi-solid alloys as a granular fluid is critical to understanding flow behaviour and defect formation during casting. Using synchrotron X-ray tomography, we directly measure the discrete grain response during uniaxial compression. We show that the stress–strain response at 64–93% solid is due to the shear-induced dilation of discrete rearranging grains. This leads to the counter-intuitive result that, in unfed samples, compression can open internal pores and draw the free surface into the liquid, resulting in cracking. A soil mechanics approach shows that, irrespective of initial solid fraction, the solid packing density moves towards a constant value during deformation, consistent with the existence of a critical state in mushy alloys analogous to soils. PMID:25034408

Importance of mechanical disaggregation in chemical weathering in a cold alpine environment, San Juan Mountains, Colorado

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.; Drever, J.I.

1999-01-01

Weathering of welded tuff near the summit of Snowshoe Mountain (3660 m) in southwestern Colorado was studied by analyzing infiltrating waters in the soil and associated solid phases. Infiltrating waters exhibit anomalously high potassium to silica ratios resulting from dissolution of a potassium-rich glass that occurs as a trace phase in the rock. In laboratory experiments using rock from the field site, initial dissolution generated potassium-rich solutions similar to those observed in the field. The anomalous potassium release decreased over time (about 1 month), after which the dominant cation was calcium, with a much lower potassium to silica ratio. The anomalous potassium concentrations observed in the infiltrating soil solutions result from weathering of freshly exposed rock surfaces. Continual mechanical disaggregation of the rock due to segregation freezing exposes fresh glass to weathering and thus maintains the source of potassium for the infiltrating water. The ongoing process of creation of fresh surfaces by physical processes is an important influence on the composition of infiltrating waters in the vadose zone.

Effect of a cationic surfactant on the volatilization of PAHs from soil.

PubMed

Lu, Li; Zhu, Lizhong

2012-06-01

Cationic surfactants are common in soils because of their use in daily cosmetic and cleaning products, and their use as a soil amendment for the mitigation and remediation of organic contaminated soils has been proposed. Such surfactant may affect the transfer and fate of organic contaminants in the environment. This study investigated the effect of a cationic surfactant, dodecylpyridinium bromide (DDPB), on the volatilization of polycyclic aromatic hydrocarbons (PAHs) from a paddy soil. The volatilization of PAHs from moist soil amended with different concentrations of DDPB was tested in an open system. The specific effects of DDPB on the liquid-vapor and solid-vapor equilibriums of PAHs were separately investigated in closed systems by headspace analysis. DDPB affects both liquid-vapor and solid-vapor processes of PAHs in soil. At DDPB concentrations below the critical micelle concentration (CMC), movement of PAHs from the bulk solution to the gas-liquid interface appeared to be facilitated by interaction between PAHs and the surfactant monomers adsorbed at the gas-liquid interface, promoting the volatilization of PAHs from solution. However, when DDPB was greater than the CMC, volatilization was inhibited due to the solubilization of PAHs by micelles. On the other hand, the formation of sorbed surfactant significantly inhibited the solid-vapor volatilization of PAHs. The overall effect of the two simultaneous effects of DDPB on liquid-vapor and solid-vapor processes was a decreased volatilization loss of PAHs from soil. Inhibition of PAH volatilization was more significant for the soil with a lower moisture content.

Simultaneous and enantioselective determination of cis-epoxiconazole and indoxacarb residues in various teas, tea infusion and soil samples by chiral high performance liquid chromatography coupled with tandem quadrupole-time-of-flight mass spectrometry.

PubMed

Zhang, Xinzhong; Luo, Fengjian; Lou, Zhengyun; Lu, Meiling; Chen, Zongmao

2014-09-12

A novel and sensitive method for simultaneous enantiomeric analysis of two pesticides-cis-epoxiconazole and indoxacarb-in various teas, black tea infusion, and soil samples has been developed. The samples were initially subjected to acetonitrile extraction followed by cleanup using lab-made florisil/graphitized carbon black mixed solid phase extraction (SPE) column (for the different teas and soil samples) and a BondElut C18-SPE column (for the black tea infusion samples). Separation of the analytes was performed on a chiral stationary phase using high performance liquid chromatography (HPLC) under a reversed-phase isocratic elution mode followed by tandem quadrupole time-of-flight mass spectrometry (Q-TOF/MS) detection. The mobile phase components, mobile phase ratios, flow rates, column temperatures, and MS parameters were all optimized to reach high sensitivity and selectivity, good peak shape, and satisfactory resolution. The performance of the method was evaluated based on the sensitivity, linearity, accuracy, precision, and matrix effects. Under optimal conditions, for the various teas (green tea, black tea, and puer tea), fresh tea leaf, soil and black tea infusion samples spiked at low, medium, and high levels, the mean recoveries for the four enantiomers ranged from 61.0% to 129.7% with most relative standard deviations (RSDs) being 17.1% or below. Good linearity can be achieved with regression coefficients (R) of 0.9915 or above for all target enantiomers, and matrix-matched calibration concentration ranging from 5.0 to 1000μg/L. The limits of detection (LODs) for all four target enantiomers were 1.4μg/kg or below in the different teas and soil samples and 0.05μg/kg or below in the black tea infusion, whereas the limits of quantification (LOQs) for those did not exceed 5.0μg/kg and 0.2μg/L, respectively. The proposed method is convenient and reliable and has been applied to real tea samples screening. It has also been extended for studies on the degradation kinetics and environmental behaviors in the field trials, providing additional information for reliable risk assessment of these chiral pesticides. Copyright © 2014 Elsevier B.V. All rights reserved.

Soil washing in combination with homogeneous Fenton-like oxidation for the removal of 2,4,4'-trichlorodiphenyl from soil contaminated with capacitor oil.

PubMed

Ma, Xiao-Hong; Zhao, Ling; Lin, Zhi-Rong; Dong, Yuan-Hua

2016-04-01

Detoxification by chemical oxidation of polychlorinated biphenyls (PCBs) in contaminated soils is very difficult and inefficient because PCBs typically associate with the solid phase or exist as non-aqueous-phase liquids due to their low solubility and slow desorption rates, and thus, they are difficult to remove from soils by using traditional, water-based elution techniques. Surfactant can enhance washing efficiency of PCBs from contaminated soils. This study used Brij 58, Brij 30, Tween 80, and 2-hydroxypropyl-β-cyclodextrin (HPCD) to solubilize 2,4,4'-trichlorodiphenyl (PCB28) from soil contaminated with capacitor oil into solution. The feasibility of PCB28 oxidation in soil washing wastewater through a Fe(3+)-catalyzed Fenton-like reaction was subsequently examined. Washing with 10 g L(-1) Brij 58 solution showed the highest extraction efficiency (up to 61.5 %) compared with that of the three other surfactants. The total concentration of PCB28 in contaminated soil at 25 °C after 48-h extraction was 286 mg L(-1). In contrast to conditions in which no washing agent was added, addition of the four washing agents decreased the efficiency of PCB28 degradation by the Fenton-like reaction, with the decrease due to addition of 10 g L(-1) Brij 58 solution being the smallest. The optimal concentration of H2O2 for preventing its useless decomposition was found to be 50 mM. The efficiency of PCB28 removal was lower when the initial concentration of PCB28 treated in the Fenton-like reaction was higher. The degradation efficiencies of PCB28 at initial concentrations of 0.1, 10, and 176 mg L(-1) in 10 g L(-1) Brij 58 solution at 25 °C and pH 3.0 and 9 h of reaction using 50 mM H2O2 were 64.1, 42.0, and 34.6 %, respectively. This result indicates that soil washing combined with Fenton-like oxidation may be a practical approach for the remediation of PCB-contaminated soil.

Characterization of EPA's 16 priority pollutant polycyclic aromatic hydrocarbons (PAHs) in tank bottom solids and associated contaminated soils at oil exploration and production sites in Texas.

PubMed

Bojes, Heidi K; Pope, Peter G

2007-04-01

The purpose of this study was to determine the concentration and types of polycyclic aromatic hydrocarbons (PAHs), a group of environmentally toxic and persistent chemicals, at contaminated oil exploration and production (E&P) sites located in environmentally sensitive and geographically distinct areas throughout Texas. Samples of tank bottom solids, the oily sediment that collects at the bottom of the tanks, were collected from inactive crude oil storage tanks at E&P sites and hydrocarbon contaminated soil samples were collected from the area surrounding each tank that was sampled. All samples were analyzed for the 16 PAH priority pollutant listed by US EPA and for total petroleum hydrocarbons (TPH). The results demonstrate that overall average PAH concentrations were significantly higher in tank bottom solids than in contaminated soils. Total PAH concentrations decreased predictably with diminishing hydrocarbon concentrations; but the percent fraction of carcinogenic PAHs per total measured PAH content increased from approximately 12% in tank bottom solids to about 46% in the contaminated soils. These results suggest that the PAH content found in tank bottom solids cannot reliably be used to predict the PAH content in associated contaminated soil. Comparison of PAHs to conservative risk-based screening levels for direct exposure to soil and leaching from soil to groundwater indicate that PAHs are not likely to exceed default risk-based thresholds in soils containing TPH of 1% (10,000mg/kg) or less. These results show that the magnitude of TPH concentration may be a useful indicator of potential risk from PAHs in crude oil-contaminated soils. The results also provide credibility to the 1% (10,000mg/kg) TPH cleanup level, used in Texas as a default management level at E&P sites located in non-sensitive areas, with respect to PAH toxicity.

Influence of Temperature, Relative Humidity, and Soil Properties on the Soil-Air Partitioning of Semivolatile Pesticides: Laboratory Measurements and Predictive Models.

PubMed

Davie-Martin, Cleo L; Hageman, Kimberly J; Chin, Yu-Ping; Rougé, Valentin; Fujita, Yuki

2015-09-01

Soil-air partition coefficient (Ksoil-air) values are often employed to investigate the fate of organic contaminants in soils; however, these values have not been measured for many compounds of interest, including semivolatile current-use pesticides. Moreover, predictive equations for estimating Ksoil-air values for pesticides (other than the organochlorine pesticides) have not been robustly developed, due to a lack of measured data. In this work, a solid-phase fugacity meter was used to measure the Ksoil-air values of 22 semivolatile current- and historic-use pesticides and their degradation products. Ksoil-air values were determined for two soils (semiarid and volcanic) under a range of environmentally relevant temperature (10-30 °C) and relative humidity (30-100%) conditions, such that 943 Ksoil-air measurements were made. Measured values were used to derive a predictive equation for pesticide Ksoil-air values based on temperature, relative humidity, soil organic carbon content, and pesticide-specific octanol-air partition coefficients. Pesticide volatilization losses from soil, calculated with the newly derived Ksoil-air predictive equation and a previously described pesticide volatilization model, were compared to previous results and showed that the choice of Ksoil-air predictive equation mainly affected the more-volatile pesticides and that the way in which relative humidity was accounted for was the most critical difference.

Identification of sensitive parameters in the modeling of SVOC reemission processes from soil to atmosphere.

PubMed

Loizeau, Vincent; Ciffroy, Philippe; Roustan, Yelva; Musson-Genon, Luc

2014-09-15

Semi-volatile organic compounds (SVOCs) are subject to Long-Range Atmospheric Transport because of transport-deposition-reemission successive processes. Several experimental data available in the literature suggest that soil is a non-negligible contributor of SVOCs to atmosphere. Then coupling soil and atmosphere in integrated coupled models and simulating reemission processes can be essential for estimating atmospheric concentration of several pollutants. However, the sources of uncertainty and variability are multiple (soil properties, meteorological conditions, chemical-specific parameters) and can significantly influence the determination of reemissions. In order to identify the key parameters in reemission modeling and their effect on global modeling uncertainty, we conducted a sensitivity analysis targeted on the 'reemission' output variable. Different parameters were tested, including soil properties, partition coefficients and meteorological conditions. We performed EFAST sensitivity analysis for four chemicals (benzo-a-pyrene, hexachlorobenzene, PCB-28 and lindane) and different spatial scenari (regional and continental scales). Partition coefficients between air, solid and water phases are influent, depending on the precision of data and global behavior of the chemical. Reemissions showed a lower variability to soil parameters (soil organic matter and water contents at field capacity and wilting point). A mapping of these parameters at a regional scale is sufficient to correctly estimate reemissions when compared to other sources of uncertainty. Copyright © 2014 Elsevier B.V. All rights reserved.

Kinetics of diuron under aerobic condition and residue analysis in sugarcane under subtropical field conditions.

PubMed

Tandon, Shishir; Pant, Ravi

2017-10-10

The phenylureas group includes persistent herbicides which are major pollutants to soil and water. Dissipation kinetics of diuron in different soils under sugarcane field conditions was investigated. Diuron was extracted with acetone and florisil solid phase extraction clean-up and characterized by high-performance liquid chromatography-UV. Diuron persisted for more than 100 days and dissipation followed monophasic first-order kinetics. Persistence was more in sandy loam compared to silty clay loam soil. Half-life of diuron in silty clay loam soil was 22.57 and 32.37 days and in sandy loam was 28.35 and 43.93 days at 2 and 4 kg ha-1applications, respectively. Average recovery in soil, bagasse, leaf-straw and juice ranged from 75.95% to 84.20%, 80.15% to 89.35%, 77.46% to 86.19% and 81.88% to 92.68%, respectively. The quantitation limits for soil, bagasse, leaf-straw and juice were 0.01, 0.03, 0.04 μg g -1 and 0.008 μg mL -1 , respectively. Application of diuron inhibited growth of soil microbes initially but they recovered later. At harvest, diuron residues were below maximum residue limits in all samples. The study revealed that under subtropical conditions, diuron is safe for use in weed management and would not pose any residual/environmental problem and that sugarcane crop could be used safe for human/animal consumption.

Polycyclic aromatic hydrocarbons bioavailability in industrial and agricultural soils: Linking SPME and Tenax extraction with bioassays.

PubMed

Guo, Meixia; Gong, Zongqiang; Li, Xiaojun; Allinson, Graeme; Rookes, James; Cahill, David

2017-06-01

The aims of this study were to evaluate the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in industrial and agricultural soils using chemical methods and a bioassay, and to study the relationships between the methods. This was conducted by comparing the quantities of PAHs extracted from two manufactured gas plant (MGP) soils and an agricultural soil with low level contamination by solid-phase micro-extraction (SPME) and Tenax-TA extraction with the quantities taken up by the earthworm (Eisenia fetida). In addition, a biodegradation experiment was conducted on one MGP soil (MGP-A) to clarify the relationship between PAH removal by biodegradation and the variation in PAH concentrations in soil pore water. Results demonstrated that the earthworm bioassay could not be used to examine PAH bioavailability in the tested MGP soils; which was the case even in the diluted MGP-A soils after biodegradation. However, the bioassay was successfully applied to the agricultural soil. These results suggest that earthworms can only be used for bioassays in soils with low toxicity. In general, rapidly desorbing concentrations extracted by Tenax-TA could predict PAH concentrations accumulated in earthworms (R 2 =0.66), while SPME underestimated earthworm concentrations by a factor of 2.5. Both SPME and Tenax extraction can provide a useful tool to predict PAH bioavailability for earthworms, but Tenax-TA extraction was proven to be a more sensitive and precise method than SPME for the prediction of earthworm exposure in the agricultural soil. Copyright © 2017. Published by Elsevier Inc.

The influence of organic substances type on the properties of mineral-organic fertilizers

NASA Astrophysics Data System (ADS)

Huculak-Mä Czka, Marta; Hoffmann, Krystyna; Hoffmann, Józef

2010-05-01

In presented research the lignite coal, peat, poultry droppings and their composts were suggested as a components of mineral-organic fertilizers. Fertility of soil is conditioned by an ability to supply plants with water and nutrients essential to their growth and development. The soil is described as tri-phase system consisting of solid, liquid and gas phase. In solid phase the soil minerals and organic matter can be distinguished. The content of micro-organisms contained in the soil i.e. microfauna and microflora is indispensable for high soil fertility. Nutrients should occur in the forms available for plants in order to obtain high yields of the high quality crops. Organic fertilizing has versatile activity. Increasing contents of humus, providing mineral nutrients included in organic substance and the improvement in physical properties of the soil belong to its main purposes. Due to applying organic fertilizers heavy soils is getting loosen and in consequence become more airy what probably influences stimulation of soil micro-organisms activity. An aqueous as well as sorption capacity of light soils is also increasing, buffer range and the stabilization of the proper level of pH value of the soil, plants are provided with basic macro and micronutrients. Conventional organic fertilizers applied in an arable farms are manure, dung, green manures and composts of different kind. Within compost group the following types can be distinguished: compost from farming, urban wastes, shredded straw, poultry droppings, industrial wastes, bark of coniferous tree etc. Properly developed fertilizer formulas should contain in their composition both mineral as well as organic elements. Such fertilizer should fit its composition to the soil and plant requirements. It should contain organic substance being characterized by a high aqueous and cations sorption capacity, substance undergoing the fast mineralization with the large calcium content. Inorganic substances e.g. bentonites which are used for suspension fertilizers manufacturing meet these requirements as well. In the presented studies lignite coal was applied as a component of mineral-organic preparations. The advantages of lignite coal are positive influence on the soil heat balance and reduction of the temperature fluctuations influence as well as humic acids contents that are extracted during its decomposition improving the soil structure and enrichment with humus substances. The lignite coal used in examinations contained 50 - 60 wt. % of Corg, about 45 cmol/kg Ca, 18.5 cmol/kg Mg and P, K, N in the ppm amount. Unfortunately the fertilizer components included in the lignite coal are rather unavailable for plants. It seems, that progress of lignite coal mineralization and humification can be expressed in the increasing content of humus substances. Humus acids are of great importance for plants on account of their solubility. During examination on the selection of fertilizer components a Corg content was analyzed as a parameter determining the quality of mineral-organic preparations. As the analytical technique for Corg determination particularly a Tiurin method was applied. Apart from lignite coal and peat as the source of organic substance the poultry droppings and compost on their basis were analyzed. Poultry droppings depending on bird species as well as feeding and breeding method are characterized by variable composition. A high pH values and a large content of nitrogen are their distinctive features, sometimes too high on account of plant nutritional requirements, and toxic as well as limiting cropping. Taking environmental protection requirements into consideration as well as on account of proper plants nutrition an appropriate preparation of mineral-organic fertilizer is recommended what can be obtained by applying lignite coal and poultry droppings as components of fertilizer using appropriate proportion. Adapting composted poultry droppings is more beneficial, but requires extra financial outlays. Results obtained from examinations of organic substance and the investigations on the influence of components on plants germination allow for developing valid formulas for mineral-organic fertilizers.

Relationship between the parent material and the soil, in plain and mountainous areas

NASA Astrophysics Data System (ADS)

Kerek, Barbara; Kuti, Laszlo; Dobos, Timea; Vatai, Jozsef; Szentpetery, Ildiko

2013-04-01

One of the most important tasks of the soil is the nutrition of plants. This function is determinated by those parts of the geological media on what is the soil situated and from what the soil was formed (those two can be different). Soil can be formed definitely just from sediment, so it is more proper to speak about parent material than parent rock. Soil forming sediment is defined as the loose sediment on the surface, which is the upper layer of near-surface rocks in flat and hilly regions, and it is the upper layer of the sediment-ensemble situated on the undisturbed bedrock in mountainous areas. Considering its origin, these sediments could be autochthon or allochton. Soil forming is determinated, besides other factors (climate, elevation, vegetation, etc.), by the parent material, which has a crucial influence on the type, quality and fertility of soils through its mineral composition, physical and chemical characteristics. Agrogeological processes happen in the superficial loose sediments in mountainous areas, but the underlying solid rock (where on the surface or close to it, there is solid rock), has an effect on them. The plain and hilly regions covered by thick loose sediment and the areas build up by solid rock and covered with thinner loose sediment in mountainous areas should be searched separately. In plain areas the near-surface formations have to be studied as a whole down to the saturated zone, but at least to 10 m. In regions of mountain and mountain fronts, the thickness, the composition and genetics of the young unconsolidated sediments situated above the older solid rocks have a vital importance, and also the relations among the soils, soil forming sediments and the base rocks have to be understood.

Selective determination of heavy metals (Cd, Pb, Cr) speciation forms from hortic anthrosols

NASA Astrophysics Data System (ADS)

Bulgariu, Dumitru; Bulgariu, Laura; Filipov, Feodor; Astefanei, Dan; Stoleru, Vasile

2010-05-01

In soils from glass houses, the speciation and inter-phases distribution processes of heavy metals have a particular dynamic, different in comparison with those from non-protected soils. The predominant distribution forms of heavy metals in such soils types are: complexes with low mass organic molecules, organic-mineral complexes, complexes with inorganic ligands (hydroxide-complexes, carbonate-complexes, sulphate-complexes, etc.) and basic salts. All of these have high stabilities in conditions of soils from glass houses, and in consequence, the separation and determination of speciation forms (which is directly connected with biodisponibility of heavy metals) by usual methods id very difficult and has a high uncertain degree. In this study is presented an original method for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils, which is based by the combination of solid-liquid sequential extraction (SPE) with the extraction in aqueous polymer-inorganic salt two-phase systems (ABS). The soil samples used for this study have been sampled from three different locations (glass houses from Iasi, Barlad and Bacau - Romania) where the vegetables cultivation have been performed by three different technologies. In this way was estimated the applicability and the analytical limits of method proposed by as, in function of the chemical-mineralogical and physical-chemical characteristics of soils. As heavy metals have been studied cadmium, lead and chromium, all being known for their high toxicity. The procedure used for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils has two main steps: (i) non-destructive separation of chemical-mineralogical associations and aggregates from soils samples - for this the separation method with heavy liquids (bromophorme) and isodynamic magnetic method have been used; (ii) sequential extraction of heavy metals from soil fractions separated in the first step, by using combined SPE-ABS procedure. For the preparation of combined extraction systems was used polyethylene glycol (with different molecular mass: 2000, 4000 and 8000). As phase-forming inorganic salts and as selective extracting agents we have used different usual inorganic reagents. The type and concentration of phase-forming salts have been selected in function of, both nature of extracted heavy metals and chemical-mineralogical characteristics of soil samples. The experimental parameters investigated in this study are: molecular mass of polyethylene glycol and the concentration of polymeric solutions, nature and concentration of phase-forming salts, nature and concentration of extracting agents, pH in extraction system phase, type of extracted heavy metals, type of speciation forms of heavy metals and their concentrations. All these factors can influence significantly the efficiency and the selectivity of separation process. The experimental results have indicate that the combined SPE-ABS extraction systems have better separation efficiency, in comparison with traditional SPE systems and ca realized a accurate discrimination between speciation forms of heavy metals from soils. Under these conditions, the estimation of inter-phases distribution and biodisponibility of heavy metals has a high precision. On the other hand, when the combined SPE-ABS systems are used, the concomitant extraction of the elements from the same geochemical association with studied heavy metals (inevitable phenomena in case of separation by SPE procedures) is significant diminished. This increases the separation selectivity and facilitated the more accurate determination of speciation forms concentration. By adequate selection of extraction conditions can be realized the selective separation of organic-mineral complexes, which will permit to perform detailed studies about the structure and chemical composition of these. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07 and project PNCDI 2 - D5 no. 52-141 / 2008).

Modeling Bacteria-Water Interactions in Soil: EPS Dynamics Under Evaporative Conditions

NASA Astrophysics Data System (ADS)

Furrer, J.; Hinestroza, H. F.; Guo, Y. S.; Gage, D. J.; Cho, Y. K.; Shor, L. M.

2017-12-01

The soil habitat represents a major linkage between the water and carbon cycles: the ability of soils to sequester or release carbon is determined primarily by soil moisture. Water retention and distribution in soils controls the abundance and activity of soil microbes. Microbes in turn impact water retention by creating biofilms, composed of extracellular polymeric substances (EPS). We model the effects of bacterial EPS on water retention at the pore scale. We use the lattice Boltzmann method (LBM), a well-established fluid dynamics modeling platform, and modify it to include the effects of water uptake and release by the swelling/shrinking EPS phase. The LB model is implemented in 2-D, with a non-ideal gas equation of state that allows condensation and evaporation of fluid in pore spaces. Soil particles are modeled according to experimentally determined particle size distributions and include realistic pore geometries, in contrast to many soil models which use spherical soil particles for simplicity. Model results are compared with evaporation experiments in soil micromodels and other simpler experimental systems, and model parameters are tuned to match experimental results. Drying behavior and solid-gel contact angle of EPS produced by the soil bacteria Sinorhizobium meliloti has been characterized and compared to the behavior of deionized water under the same conditions. The difference in behavior between the fluids is used to parameterize the model. The model shows excellent qualitative agreement for soil micromodels with both aggregated and non-aggregated particle arrangements under no-EPS conditions, and reproduces realistic drying behavior for EPS. This work represents a multi-disciplinary approach to understanding microbe-soil interactions at the pore scale.

Concentrations of trace elements and PCDD/Fs around a municipal solid waste incinerator in Girona (Catalonia, Spain). Human health risks for the population living in the neighborhood.

PubMed

Rovira, Joaquim; Nadal, Martí; Schuhmacher, Marta; Domingo, José L

2018-07-15

Previously to the modernization of the municipal solid waste incinerator (MSWI) of Campdorà (Girona, Catalonia, Spain) two sampling campaigns (2015 and 2016) were conducted. In each campaign, 8 soil and 4 air samples (PM 10 and total particle phase and gas phase) were collected. The levels of As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Sn, Tl and V, and PCDD/Fs were analysed at different distances and wind directions around the MSWI. Environmental levels of trace elements and PCDD/Fs were used to assess exposure and health risks (carcinogenic and non-carcinogenic) for the population living around the facility. In soils, no significant differences were observed for trace elements and PCDD/Fs between both campaigns. In air, significant higher levels of As, Cd, Co, Mn, Ni, Pb, Tl and V were detected in 2016. Regarding soil levels, only Cd (distances) and As, Cu, Mn, and Ni (wind directions) showed significant differences. No differences were noted in the concentrations of trace elements and PCDD/Fs in air levels with respect to distances and directions to the MSWI. No differences were registered in air levels (elements and PCDD/Fs) between points influenced by MSWI emissions and background point. However some differences in congener profile were noted regarding from where back-trajectories come from (HYSPLIT model results), pointing some influence of Barcelona metropolitan area. The concentrations of trace elements and PCDD/Fs were similar -or even lower- than those reported around other MSWIs in Catalonia and various countries. Non-carcinogenic risks were below the safety limit (HQ<1). In turn, carcinogenic risks due to exposure to trace elements and PCDD/Fs were in acceptable ranges, according to national and international standard regulations. Copyright © 2018 Elsevier B.V. All rights reserved.

On-site comprehensive analysis of explosives using HPLC-UV-PAED

NASA Astrophysics Data System (ADS)

Marple, Ronita L.; LaCourse, William R.

2004-03-01

High-performance liquid chromatography with ultra violet and photo-assisted electrochemical detection (HPLC-UV-PAED) has been developed for the sensitive and selective detection of explosives in ground water and soil extracts. Fractionation and preconcentration of explosives is accomplished with on-line solid phase extraction (SPE), which minimizes sample pretreatment and enables faster and more accurate on-site assessment of a contaminated site. Detection limits are equivalent or superior (i.e., <1 part-per-trillion for HMX) to those achieved using the Environmental Protection Agency (EPA) Method 8330. This approach is more broadly applicable, as it is capable of determining a wider range of organic nitro compounds. Soil samples are extracted using pressurized fluid extraction (PFE), and this technique is automatable, field-compatible, and environmentally friendly, adding to the overall efficiency of the methodology.

On-line separation and preconcentration of lead(II) by solid-phase extraction using activated carbon loaded with xylenol orange and its determination by flame atomic absorption spectrometry.

PubMed

Ensafi, Ali A; Shiraz, A Zendegi

2008-02-11

Activated carbon loaded with xylenol orange in a mini-column was used for the highly selective separation and preconcentration of Pb(II) ions. An on-line system for enrichment and the determination of Pb(II) was carried out on flame atomic absorption spectrometry. The conditions of preconcentration and quantitative recovery of Pb(II) from diluted solution, such as pH of aqueous phase, amount of the sorbent, volume of the solutions and flow variables were studied as well as effect of potential interfering ions. Under the optimum conditions, Pb(II) in an aqueous sample was concentrated about 200-fold and the detection limit was 0.4 ng mL(-1) Pb(II). The adsorption capacity of the solid phase was 0.20mg of lead per one gram of the modified activated carbon. The modified activated carbon is stable for several treatments of sample solutions without the need for using any chemical reagent. The recovery of lead(II) from river water, waste water, tap water, and in the following reference materials: SRM 2711 Montana soil and GBW-07605 tea were obtained in the range of 97-104% by the proposed method.

Kinetics of mercuric chloride retention by soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amacher, M.C.; Selim, H.M.; Iskandar, I.K.

A nonlinear multireaction model was used to describe kinetic data for HgCl{sub 2} retention by five soils. A three-parameter version of the model consisting of a reversible nonlinear (nth order, n < 1) reaction and an irreversible first-order reaction was capable of describing HgCl{sub 2} retention data for Cecil (clayey, kaolinitic, thermic Typic Kanhapludult) and Windsor (mixed, mesic Typic Udipsamment) soils at all initial solution Hg concentrations, and data for Norwood, (fine-silty, mixed (calcareous), thermic, Typic Udifluvent), Olivier (fine-silty, mixed, thermic Aquic Fragiudalt), and Sharkey (very-fine, montmorillonitic, nonacid, thermic Vertic Haplaquept) soils at initial solution Hg concentrations below 5 mg/L.more » A five-parameter version of the model, with an added reversible nonlinear reaction, provided a more accurate description of the retention data for the Norwood, Olivier, and Sharkey soils at initial solution Hg concentrations above 5 mg/L. The second reaction needed to describe the data at higher Hg concentrations suggests the presence of a second type of sorption sites, or a precipitation or coprecipitation reaction not encountered at lower Hg concentrations. Release of Hg from the soils was induced by serial dilution of the soil solution, but not all the soil Hg was reversibly retained. This was also indicated by the model. Release of soil Hg depended on the concentration of retained Hg with significant Hg release occurring only at high concentrations of retained Hg. A multireaction model is needed to describe Hg retention in soils because of the many solid phases that can remove Hg from solution.« less

Role of an organic carbon-rich soil and Fe(III) reduction in reducing the toxicity and environmental mobility of chromium(VI) at a COPR disposal site.

PubMed

Ding, Weixuan; Stewart, Douglas I; Humphreys, Paul N; Rout, Simon P; Burke, Ian T

2016-01-15

Cr(VI) is an important contaminant found at sites where chromium ore processing residue (COPR) is deposited. No low cost treatment exists for Cr(VI) leaching from such sites. This study investigated the mechanism of interaction of alkaline Cr(VI)-containing leachate with an Fe(II)-containing organic matter rich soil beneath the waste. The soil currently contains 0.8% Cr, shown to be present as Cr(III)(OH)3 in EXAFS analysis. Lab tests confirmed that the reaction of Cr(VI) in site leachate with Fe(II) present in the soil was stoichiometrically correct for a reductive mechanism of Cr accumulation. However, the amount of Fe(II) present in the soil was insufficient to maintain long term Cr(VI) reduction at historic infiltration rates. The soil contains a population of bacteria dominated by a Mangroviflexus-like species, that is closely related to known fermentative bacteria, and a community capable of sustaining Fe(III) reduction in alkaline culture. It is therefore likely that in situ fermentative metabolism supported by organic matter in the soil produces more labile organic substrates (lactate was detected) that support microbial Fe(III) reduction. It is therefore suggested that addition of solid phase organic matter to soils adjacent to COPR may reduce the long term spread of Cr(VI) in the environment. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Investigation of sterols as potential biomarkers for the detection of pig (S. s. domesticus) decomposition fluid in soils.

PubMed

von der Lühe, Barbara; Dawson, Lorna A; Mayes, Robert W; Forbes, Shari L; Fiedler, Sabine

2013-07-10

This study was carried out to evaluate the potential of using cholesterol and coprostanol, as indicators for the detection of decomposition fluid of buried pigs (S. s. domesticus) in soils. In May 2007, four pig carcasses (∼35kg) were buried in shallow graves (∼40 cm depth) at the University of Ontario Institute of Technology in Canada. Two pigs were exhumed after three months (Pig 1, Pig 2) and six months (Pig 3, Pig 4) post burial. Soil samples were collected beneath the pig carcasses (∼40cm depth) and from grave walls (∼15-20 cm depth) as well as from a parallel control site. Coprostanol and cholesterol were extracted from soils, purified with solid phase extraction (SPE) and analysed with gas chromatography/mass spectrometry (GC/MS). A significant increase in cholesterol concentrations (p<0.05) and amounts of coprostanol were detected in soil located beneath the pig carcasses after three months of burial. It is assumed that during the putrefaction and liquefaction stages of decomposition pig fluid which contains cholesterol and coprostanol is released into the underlying soil. Therefore, cholesterol and coprostanol could be used as potential biomarkers to detect the presence of decomposition fluid three months after burial under comparable soil and environmental conditions. Further research is suggested for additional soil sampling before and after three months to investigate the abundance of these and other sterols. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Microbial-driven arsenic cycling in rice paddies amended with monosodium methanearsonate

NASA Astrophysics Data System (ADS)

Maguffin, S. C.; McClung, A.; Rohila, J. S.; Derry, L. A.; Huang, R.; Reid, M. C.

2017-12-01

Rice consumption is the second largest contributor to human arsenic exposure worldwide and is linked to many serious diseases. Because rice is uniquely adapted for agricultural production under flooded soils, arsenic species solubilized in such environments can be effectively transported into plant tissue via root transporters. Through this process, both inorganic and organic (methylated) arsenic species can accumulate to problematic concentrations and may affect grain yield as well as crop value. The distribution of these species in plant tissue is determined by arsenic sources, as well as enzymatic redox and methylation-demethylation reactions in soils and pore water. Historic use of organoarsenic-based pesticides in US agriculture may provide an enduring source of arsenic in rice paddies. However, it is unclear how persistent these organic species are in the adsorbed phase or how available they remain to rice cultivars throughout the growing season. We conducted a field experiment in a 2x2 factorial design examining the effects of irrigation methods (continuous flooding and alternate wetting and drying) and monosodium methanearsonate (MSMA) application on the abundance and speciation of arsenic in pore water, soil, and rice plant tissues. We monitored arsenic speciation and partitioning between these reservoirs at semi-weekly to semi-monthly frequencies. Pore water arsenic speciation was determined using LC-ICP-MS, and X-ray absorption near-edge structure (XANES) analysis was employed to speciate the arsenic within solid-phase soil and plant tissue throughout the growing season. These data help clarify the role of two irrigation methods and MSMA amendments for arsenic bioavailability and speciation in rice. Furthermore, the study illuminates the significance of microbial metabolism in the reapportionment of arsenic within the soil-plant-water system and its impact on arsenic levels in rice grains.

Clay fractions from a soil chronosequence after glacier retreat reveal the initial evolution of organo-mineral associations

NASA Astrophysics Data System (ADS)

Dümig, Alexander; Häusler, Werner; Steffens, Markus; Kögel-Knabner, Ingrid

2012-05-01

Interactions between organic and mineral constituents prolong the residence time of organic matter in soils. However, the structural organization and mechanisms of organic coverage on mineral surfaces as well as their development with time are still unclear. We used clay fractions from a soil chronosequence (15, 75 and 120 years) in the foreland of the retreating Damma glacier (Switzerland) and from mature soils outside the proglacial area (>700 and <3000 years) to elucidate the evolution of organo-mineral associations during initial soil formation. The chemical composition of the clay-bound organic matter (OM) was assessed by solid-state 13C NMR spectroscopy while the quantities of amino acids and neutral sugar monomers were determined after acid hydrolysis. The mineral phase was characterized by X-ray diffraction, oxalate extraction, specific surface area by N2 adsorption (BET approach), and cation exchange capacity at pH 7 (CECpH7). The last two methods were applied before and after H2O2 treatment. We found pronounced shifts in quantity and quality of OM during aging of the clay fractions, especially within the first one hundred years of soil formation. The strongly increasing organic carbon (OC) loading of clay-sized particles resulted in decreasing specific surface areas (SSA) of the mineral phases and increasing CECpH7. Thus, OC accumulation was faster than the supply of mineral surfaces and cation exchange capacity was mainly determined by the OC content. Clay-bound OC of the 15-year-old soils showed high proportions of carboxyl C and aromatic C. This may point to remnants of ancient OC which were inherited from the recently exposed glacial till. With increasing age (75 and 120 years), the relative proportions of carboxyl and aromatic C decreased. This was associated with increasing O-alkyl C proportions, whereas accumulation of alkyl C was mainly detected in clay fractions from the mature soils. These findings from solid-state 13C NMR spectroscopy are in line with the increasing amounts of microbial-derived carbohydrates with soil age. The large accumulation of proteins, which was comparable to those of carbohydrates, and the very low C/N ratios of H2O2-resistant OM indicated strong and preferential associations between proteinaceous compounds and mineral surfaces. In the acid soils, poorly crystalline Fe oxides were the main providers of mineral surface area and important for the stabilization of OM during aging of the clay fractions. This was indicated by (I) the strong correlations between oxalate soluble Fe and both, SSA of H2O2-treated clay fractions and OC content, and (II) the low formation of expandable clays due to small extents of mineral weathering. Our chronosequence approach provided new insights into the evolution of organo-mineral interactions in acid soils. The formation of organo-mineral associations started with the sorption of proteinaceous compounds and microbial-derived carbohydrates on mineral surfaces which were mainly provided by ferrihydrite. The sequential accumulation of different organic compounds and the large OC loadings point to multiple accretion of OM in distinct zones or layers during the initial evolution of clay fractions.

Quantitative determination of acidic hydrolysis products of Chemical Weapons Convention related chemicals from aqueous and soil samples using ion-pair solid-phase extraction and in situ butylation.

PubMed

Pal Anagoni, Suresh; Kauser, Asma; Maity, Gopal; Upadhyayula, Vijayasarathi V R

2018-02-01

Chemical warfare agents such as organophosphorus nerve agents, mustard agents, and psychotomimetic agent like 3-quinuclidinylbenzilate degrade in the environment and form acidic degradation products, the analysis of which is difficult under normal analytical conditions. In the present work, a simultaneous extraction and derivatization method in which the analytes are butylated followed by gas chromatography and mass spectrometric identification of the analytes from aqueous and soil samples was carried out. The extraction was carried out using ion-pair solid-phase extraction with tetrabutylammonium hydroxide followed by gas chromatography with mass spectrometry in the electron ionization mode. Various parameters such as optimum concentration of the ion-pair reagent, pH of the sample, extraction solvent, and type of ion-pair reagent were optimized. The method was validated for various parameters such as linearity, accuracy, precision, and limit of detection and quantification. The method was observed to be linear from 1 to 1000 ng/mL range in selected ion monitoring mode. The extraction recoveries were in the range of 85-110% from the matrixes with the limit of quantification for alkyl phosphonic acids at 1 ng/mL, thiodiglycolic acid at 20 ng/mL, and benzilic acid at 50 ng/mL with intra- and interday precisions below 15%. The developed method was applied for the samples prepared in the scenario of challenging inspection. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The fate of arsenic adsorbed on iron oxides in the presence of arsenite-oxidizing bacteria.

PubMed

Zhang, Zhennan; Yin, Naiyi; Du, Huili; Cai, Xiaolin; Cui, Yanshan

2016-05-01

Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on its oxidation state. Arsenite [As(III)] can be oxidized by microbes and adsorbed by minerals in the soil. However, the combined effects of these abiotic and biotic processes are not well understood. In this study, the fate of arsenic in the presence of an isolated As(III)-oxidizing bacterium (Pseudomonas sp. HN-1, 10(9) colony-forming units (CFUs)·ml(-1)) and three iron oxides (goethite, hematite, and magnetite at 1.6 g L(-1)) was determined using batch experiments. The total As adsorption by iron oxides was lower with bacteria present and was higher with iron oxides alone. The total As adsorption decreased by 78.6%, 36.0% and 79.7% for goethite, hematite and magnetite, respectively, due to the presence of bacteria. As(III) adsorbed on iron oxides could also be oxidized by Pseudomonas sp. HN-1, but the oxidation rate (1.3 μmol h(-1)) was much slower than the rate in the aqueous phase (96.2 μmol h(-1)). Therefore, the results of other studies with minerals only might overestimate the adsorptive capacity of solids in natural systems; the presence of minerals might hinder As(III) oxidation by microbes. Under aerobic conditions, in the presence of iron oxides and As(III)-oxidizing bacteria, arsenic is adsorbed onto iron oxides within the adsorption capacity, and As(V) is the primary form in the solid and aqueous phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

Phytoscreening as an efficient tool to delineate chlorinated solvent sources at a chlor-alkali facility.

PubMed

Yung, Loïc; Lagron, Jérôme; Cazaux, David; Limmer, Matt; Chalot, Michel

2017-05-01

Chlorinated ethenes (CE) are among the most common volatile organic compounds (VOC) that contaminate groundwater, currently representing a major source of pollution worldwide. Phytoscreening has been developed and employed through different applications at numerous sites, where it was generally useful for detection of subsurface chlorinated solvents. We aimed at delineating subsurface CE contamination at a chlor-alkali facility using tree core data that we compared with soil data. For this investigation a total of 170 trees from experimental zones was sampled and analyzed for perchloroethene (PCE) and trichloroethene (TCE) concentrations, measured by solid phase microextraction gas chromatography coupled to mass spectrometry. Within the panel of tree genera sampled, Quercus and Ulmus appeared to be efficient biomonitors of subjacent TCE and PCE contamination, in addition to the well known and widely used Populus and Salix genera. Among the 28 trees located above the dense non-aqueous phase liquid (DNAPL) phase zone, 19 tree cores contained detectable amounts of CE, with concentrations ranging from 3 to 3000 μg L -1 . Our tree core dataset was found to be well related to soil gas sampling results, although the tree coring data were more informative. Our data further emphasized the need for choosing the relevant tree species and sampling periods, as well as taking into consideration the nature of the soil and its heterogeneity. Overall, this low-invasive screening method appeared useful to delineate contaminants at a small-scale site impacted by multiple sources of chlorinated solvents. Copyright © 2017 Elsevier Ltd. All rights reserved.

Non-composted municipal solid waste byproduct influences soil and plant nutrients five years after soil reclamation

USDA-ARS?s Scientific Manuscript database

Concerns for the mounting supply of municipal solid waste being generated combined with decreasing landfill space have compelled military installations to evaluate alternative methods for disposal. One approach to reduce landfilling is the use of a new garbage-processing technology that sterilizes a...

Trace Metals and Nutrients at the Soil-Root Interface of Forest Soils

NASA Astrophysics Data System (ADS)

Courchesne, F.; Seguin, V.; Legrand, P.; Cloutier-Hurteau, B.

2004-05-01

The activity of roots creates a microenvironment, known as the rhizosphere, where soil properties, processes and feedback mechanisms differ substantially from those observed in the soil matrix. Due to its proximity to the site of elemental uptake by plants, the rhizosphere is viewed as a biogeochemical hotspot characterized by massive fluxes of matter and energy. In this context, the acquisition of new knowledge on the rhizosphere is crucial to increase our capacity to understand, manage and model soil-plants systems. Of particular interest to scientists is the response of the rhizosphere to perturbations of natural (e.g. climatic fluctuations) or anthropogenic (e.g. soil contamination) origin. Moreover, results from rhizosphere research help define new approaches designed either to restrict the entrance of potentially toxic elements in crops and, hence, in the food chain or, contrarily, to increase the uptake of trace elements by plants in contaminated environments to be bioremediated. Our recent studies in forested environments have clearly established that the rhizosphere (Abies, Acer, Betula, Picea, Pinus or Populus roots) is more acidic than the soil matrix and that it is enriched in organic substances (dissolved and solid), nutrient cations (Ca, Mg) and trace metals. Indeed, the rhizosphere systematically acts as a sink for Cd, Cu, Ni, Pb and Zn, notably under bioavailable (water-soluble and salt-extractable) forms. Yet, the relative activity of free metal ions is lower in the rhizosphere, as shown for Cu++, probably as a consequence of the higher DOC content. The corrosive environment forming in the rhizosphere, as controlled by the release of H+ ions and of organic acids, also impacts on mineral assemblages through an increase in the weathering of primary minerals (amphiboles, plagioclases) and the formation of secondary solid phases such as Fe and Al oxides. Some of the research avenues currently investigated by our research group include the quantification of functional links between organic carbon, microbial activity and metal speciation, the development of methodological and analytical approaches operating at the spatial scale of the rhizosphere and, the assessment of preferential hydrological fluxes along root networks.

Influence of a nonionic surfactant (Triton X-100) on contaminant distribution between water and several soil solids

USGS Publications Warehouse

Lee, J.-F.; Liao, P.-M.; Kuo, C.-C.; Yang, H.-T.; Chiou, C.T.

2000-01-01

The influence of a nonionic surfactant (Triton X-100) on the contaminant distribution coefficients in solid-water mixtures was determined for a number of relatively nonpolar compounds (contaminants) on several natural solids. The studied compounds consisted of BTEX (benzene, toluene, ethylbenzene, and p-xylene) and chlorinated pesticides (lindane, ??-BHC, and heptachlor epoxide), which span several orders of magnitude in water solubility (S(W)); the solid samples comprised a bentonite, a peat, and two other soils, which cover a wide range of solid organic matter (SOM) content. The applied surfactant concentrations (X) ranged from below the (nominal) CMC to 2-3 times the CMC. For relatively water-soluble BTEX compounds, the distribution coefficients with surfactant (K*(d)) all exceeded those without surfactant (K(d)); the K*(d)/K(d) ratios increased with increasing S(w) from p-xylene to benzene on each solid at a given X, with increasing X for each compound on a solid, and with decreasing solid SOM content for each compound over the range of X studied. For the less-soluble pesticides, the K*(d)/K(d) ratios exhibited a large increase with X for bentonite, a marginal change (increase or decrease) for a soil of 2.4% SOM, and a moderate-to-large decrease for two soils of 14.8% and 86.4% SOM. These unique observations were rationalized in terms of the properties of the compound, the amount of surfactant sorbed on the solid, the enhanced solubilization of the compound by surfactant in water, and the relative effects of the surfactant when adsorbed on minerals and when partitioned into SOM. (C) 2000 Academic Press.

Organic Matter Transformation in the Peat Column at Marcell Experimental Forest: Humification and Vertical Stratification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tfaily, Malak; Cooper, Bill; Kostka,

2014-01-01

A large-scale ecosystem manipulation (Spruce and Peatland Responses under Climatic and Environmental Change, SPRUCE) is being constructed in the Marcell Experimental Forest, Minnesota, USA, to determine the effects of climatic forcing on ecosystem processes in northern peatlands. Prior to the initiation of the manipulation, we characterized the solid-phase peat to a depth of 2 meters using a variety of techniques, including peat C:N ratios, 13C and 15N isotopic composition, Fourier Transform Infrared (FT IR), and 13C Nuclear Magnetic Resonance spectroscopy (13C NMR). FT IR determined peat humification-levels increased rapidly between and 75 cm, indicating a highly reactive zone. We observedmore » a rapid drop in the abundance of O-alkyl-C, carboxyl-C, and other oxygenated functionalities within this zone and a concomitant increase in the abundance of alkyl- and nitrogen-containing compounds. Below 75-cm, minimal change was observed except that aromatic functionalities accumulated with depth. Incubation studies revealed the highest methane production rates and greatest CH4:CO2 ratios within this and 75 cm zone. Hydrology and surface vegetation played a role in belowground carbon cycling. Radiocarbon signatures of microbial respiration products in deeper porewaters resembled the signatures of dissolved organic carbon rather than solid phase peat, indicating that more recently photosynthesized organic matter fueled the bulk of subsurface microbial respiration. Oxygen-containing functionalities, especially O-alkyl-C, appear to serve as an excellent proxy for soil decomposition rate, and in addition should be a sensitive indicator of the response of the solid phase peat to the climatic manipulation.« less

Determination of isoxaflutole (balance) and its metabolites in water using solid phase extraction followed by high-performance liquid chromatography with ultraviolet or mass spectrometry

USGS Publications Warehouse

Lin, Chung-Ho; Lerch, Robert N.; Thurman, E. Michael; Garrett , Harold E.; George, Milon F.

2002-01-01

Balance (isoxaflutole, IXF) belongs to a new family of herbicides referred to as isoxazoles. IXF has a very short soil half-life (<24 h), degrading to a biologically active diketonitrile (DKN) metabolite that is more polar and considerably more stable. Further degradation of the DKN metabolite produces a nonbiologically active benzoic acid (BA) metabolite. Analytical methods using solid phase extraction followed by high-performance liquid chromatography−UV (HPLC-UV) or high-performance liquid chromatography−mass spectrometry (HPLC-MS) were developed for the analysis of IXF and its metabolites in distilled deionized water and ground water samples. To successfully detect and quantify the BA metabolite by HPLC-UV from ground water samples, a sequential elution scheme was necessary. Using HPLC-UV, the mean recoveries from sequential elution of the parent and its two metabolites from fortified ground water samples ranged from 68.6 to 101.4%. For HPLC-MS, solid phase extraction of ground water samples was performed using a polystyrene divinylbenzene polymer resin. The mean HPLC-MS recoveries of the three compounds from ground water samples spiked at 0.05−2 μg/L ranged from 100.9 to 110.3%. The limits of quantitation for HPLC-UV are approximately 150 ng/L for IXF, 100 ng/L for DKN, and 250 ng/L for BA. The limit of quantitation by HPLC-MS is 50 ng/L for each compound. The methods developed in this work can be applied to determine the transport and fate of Balance in the environment.

Determination of isoxaflutole (balance) and its metabolites in water using solid phase extraction followed by high-performance liquid chromatography with ultraviolet or mass spectrometry.

PubMed

Lin, Chung-Ho; Lerch, Robert N; Thurman, E Michael; Garrett, Harold E; George, Milon F

2002-10-09

Balance (isoxaflutole, IXF) belongs to a new family of herbicides referred to as isoxazoles. IXF has a very short soil half-life (<24 h), degrading to a biologically active diketonitrile (DKN) metabolite that is more polar and considerably more stable. Further degradation of the DKN metabolite produces a nonbiologically active benzoic acid (BA) metabolite. Analytical methods using solid phase extraction followed by high-performance liquid chromatography-UV (HPLC-UV) or high-performance liquid chromatography-mass spectrometry (HPLC-MS) were developed for the analysis of IXF and its metabolites in distilled deionized water and ground water samples. To successfully detect and quantify the BA metabolite by HPLC-UV from ground water samples, a sequential elution scheme was necessary. Using HPLC-UV, the mean recoveries from sequential elution of the parent and its two metabolites from fortified ground water samples ranged from 68.6 to 101.4%. For HPLC-MS, solid phase extraction of ground water samples was performed using a polystyrene divinylbenzene polymer resin. The mean HPLC-MS recoveries of the three compounds from ground water samples spiked at 0.05-2 microg/L ranged from 100.9 to 110.3%. The limits of quantitation for HPLC-UV are approximately 150 ng/L for IXF, 100 ng/L for DKN, and 250 ng/L for BA. The limit of quantitation by HPLC-MS is 50 ng/L for each compound. The methods developed in this work can be applied to determine the transport and fate of Balance in the environment.

Impact of biostimulated redox processes on metal dynamics in an iron-rich creek soil of a former uranium mining area.

PubMed

Burkhardt, Eva-Maria; Akob, Denise M; Bischoff, Sebastian; Sitte, Jana; Kostka, Joel E; Banerjee, Dipanjan; Scheinost, Andreas C; Küsel, Kirsten

2010-01-01

Understanding the dynamics of metals and radionuclides in soil environments is necessary for evaluating risks to pristine sites. An iron-rich creek soil of a former uranium-mining district (Ronneburg, Germany) showed high porewater concentrations of heavy metals and radionuclides. Thus, this study aims to (i) evaluate metal dynamics during terminal electron accepting processes (TEAPs) and (ii) characterize active microbial populations in biostimulated soil microcosms using a stable isotope probing (SIP) approach. In biostimulated soil slurries, concentrations of soluble Co, Ni, Zn, As, and unexpectedly U increased during Fe(III)-reduction. This suggests that there was a release of sorbed metals and As during reductive dissolution of Fe(III)-oxides. Subsequent sulfate-reduction was concurrent with a decrease of U, Co, Ni, and Zn concentrations. The relative contribution of U(IV) in the solid phase changed from 18.5 to 88.7% after incubation. The active Fe(III)-reducing population was dominated by delta-Proteobacteria (Geobacter) in (13)C-ethanol amended microcosms. A more diverse community was present in (13)C-lactate amended microcosms including taxa related to Acidobacteria, Firmicutes, delta-Proteobacteria, and beta-Proteobacteria. Our results suggested that biostimulated Fe(III)-reducing communities facilitated the release of metals including U to groundwater which is in contrast to other studies.

Remediation of heavy hydrocarbon impacted soil using biopolymer and polystyrene foam beads.

PubMed

Wilton, Nicholas; Lyon-Marion, Bonnie A; Kamath, Roopa; McVey, Kevin; Pennell, Kurt D; Robbat, Albert

2018-05-05

A green chemistry solution is presented for the remediation of heavy hydrocarbon impacted soils. The two-phase recovery system relies on a plant-based biopolymer, which releases hydrocarbons from soil, and polystyrene foam beads, which recover them from solids and water. The efficiency of the process was demonstrated by comparisons with control experiments, where water, biopolymer, or beads alone yielded total petroleum hydrocarbon (TPH) reductions of 25%, 52%, and 58%, respectively, compared to 94% when 1.25 mL of 1% biopolymer and 15 mg beads per gram of soil were agitated for 30 min. Reductions in TPH content were substantial regardless of soil fraction, with removals of 97%, 91%, and 75% from sand, silt, and clay size fractions, respectively. Additionally, treatment efficiency was independent of carbon number, C 13 to C 43 , as demonstrated by reductions in both diesel fuel (C 13 -C 28 ) and residual-range organics (C 25 -C 43 ) of ∼90%. Compared to other published polymer- and surfactant-based treatment methods, this system requires less mobilizing agent, sorbent, and mixing time. The remediation process is both efficient and sustainable because the biopolymer is re-useable and sourced from renewable crops and polystyrene beads are obtained from recycled materials. Copyright © 2018 Elsevier B.V. All rights reserved.

Solubility and transport of Cr(III) in a historically contaminated soil - Evidence of a rapidly reacting dimeric Cr(III) organic matter complex.

PubMed

Löv, Åsa; Sjöstedt, Carin; Larsbo, Mats; Persson, Ingmar; Gustafsson, Jon Petter; Cornelis, Geert; Kleja, Dan B

2017-12-01

Chromium is a common soil contaminant and, although it has been studied widely, questions about its speciation and dissolutions kinetics remain unanswered. We combined information from an irrigation experiment performed with intact soil columns with data from batch experiments to evaluate solubility and mobilization mechanisms of Cr(III) in a historically contaminated soil (>65 years). Particulate and colloidal Cr(III) forms dominated transport in this soil, but their concentrations were independent of irrigation intensity (2-20 mm h -1 ). Extended X-ray absorption fine structure (EXAFS) measurements indicated that Cr(III) associated with colloids and particles, and with the solid phase, mainly existed as dimeric hydrolyzed Cr(III) bound to natural organic matter. Dissolution kinetics of this species were fast (≤1 day) at low pH (<3) and slightly slower (≤5 days) at neutral pH. Furthermore, it proved possible to describe the solubility of the dimeric Cr(III) organic matter complex with a geochemical equilibrium model using only generic binding parameters, opening the way for use of geochemical models in risk assessments of Cr(III)-contaminated sites. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Evaluation of PAH contamination in soil treated with solid by-products from shale pyrolysis.

PubMed

Nicolini, Jaqueline; Khan, Muhammad Y; Matsui, M; Côcco, Lílian C; Yamamoto, Carlos I; Lopes, Wilson A; de Andrade, Jailson B; Pillon, Clenio N; Arizaga, Gregorio G Carbajal; Mangrich, Antonio S

2015-01-01

The aim of this work was to evaluate the concentrations of polycyclic aromatic hydrocarbons (PAHs) in soils to which solid shale materials (SSMs) were added as soil conditioners. The SSMs were derived from the Petrosix pyrolysis process developed by Petrobras (Brazil). An improved ultrasonic agitation method was used to extract the PAHs from the solid samples (soils amended with SSMs), and the concentrations of the compounds were determined by gas chromatography coupled to mass spectrometry (GC-MS). The procedure provided satisfactory recoveries, detection limits, and quantification limits. The two-, three-, and four-ring PAHs were most prevalent, and the highest concentration was obtained for phenanthrene (978 ± 19 μg kg(-1) in a pyrolyzed shale sample). The use of phenanthrene/anthracene and fluoranthene/pyrene ratios revealed that the PAHs were derived from petrogenic rather than pyrogenic sources. The measured PAH concentrations did not exceed national or international limit values, suggesting that the use of SSMs as soil conditioners should not cause environmental damage.

Safe and High Quality Food Production using Low Quality Waters and Improved Irrigation Systems and Management (SAFIR)

NASA Astrophysics Data System (ADS)

Cary, L.; Kloppmann, W.; Battilani, A.; Bertaki, M.; Blagojevic, S.; Chartzoulakis, K.; Dalsgaard, A.; Forslund, A.; Jovanovic, Z.; Kasapakis, I.

2009-04-01

The safe use of treated domestic wastewater for irrigation needs to address the risks for humans (workers, exposed via contact with irrigation water, soil, crops and food, consumers, exposed via ingestion of fresh and processed food), for animals (via ingestion of crops an soil), for the crops and agricultural productivity (via salinity and trace element uptake), for soil (via accumulation or release of pollutants) as well as for surface, groundwaters and the associated ecosystems (via runoff and infiltration, Kass et al., 2005, Bouwer, 2000). A work package in the EU FP5 project SAFIR is dedicated to study the impact of wastewater irrigation on the soil-water-plant-product system. Its monitoring program comprises pathogens and inorganic pollutants, including both geogenic and potentially anthropogenic trace elements in the aim to better understand soil-irrigation water interactions. The SAFIR field study sites are found in China, Italy, Crete, and Serbia. A performance evaluation of SAFIR-specific treatment technology through the monitoring of waste water and irrigation water quality was made through waste water chemical and microbiological qualities, which were investigated upstream and downstream of the SAFIR specific treatment three times per season. Irrigation water transits through the uppermost soil decimetres to the crop roots. The latter will become, in the course of the irrigation season, the major sink of percolating water, together with evaporation. The water saving irrigation techniques used in SAFIR are surface and subsurface drip irrigation. The investigation of the solid soil phase concentrates on the root zone as main transit and storage compartment for pollutants and, eventually, pathogens. The initial soil quality was assessed through a sampling campaign before the onset of the first year irrigation; the soil quality has been monitored throughout three years under cultivation of tomatoes or potatoes. The plot layout for each of the study sites allows comparing different combinations of (1) water quality, including tap water as a reference, (2) irrigation techniques, and (3) irrigation strategies (including full irrigation, partial root drying, RDI). The replication of each of the combinations on three different plots takes into account the local variations of soil properties and allows a proper statistical treatment. Reactions of the infiltrating water with the soil solid phase are important for the solute cycling, temporary fixation and remobilisation of trace pollutants. The type of reaction (sorption, co-precipitation…) and the reactive mineral phases will also determine the availability of trace elements for the plant and determine the passage towards crops and products. Therefore it is important to assess the soil water quality, directly or indirectly. Direct measurements of soil water imply soil water sampling through an appropriate system; porous cups were installed on the Cretan, Italian and Chinese sites. Indirect evaluation of water-soil interactions can be obtained through sequential extractions. The combination of a variable input function (through diffuse pollution, irrigation, fertigation) and of variable MTE mobility in soils can be expected to lead to short term variations in soil metal concentrations even if such short term variations have been rarely investigated (Féder, 2001; Cary and Trolard, 2008). The sampling focused upon the fully irrigated plots given that the potential impact of irrigation water quality on soil and plant quality can be expected higher for fully irrigated soils compared to other irrigation strategies. Samples were taken within the soil volume of potential influence around each of the drip emitters. This volume varies depending on the nature of the soil and the irrigation system so that each site adopted a specific protocol. For all experiments, three sampling campaigns were scheduled for each irrigation season: at pre-planting, at the end of irrigation, at harvest. The geochemical evolution of soil properties over the 3 years shows significant variations in major and minor elements, especially trace metallic elements. It implies the role of the cultivated plant as a sink of elements which leads to direct loss of elements in the soil system. Bouwer, H., 2000. Groundwater problems caused by irrigation with sewage effluent. Journal of Environmental Health 63, 17-20. Cary L., Trolard F. (2008). Metal mobility in the ground water of a paddy field in Camargue (South eastern France). Journal of Geochemical Exploration 96/2-3 : 132-143. Féder, 2001. Dynamique des processus d'oxydo-reduction dans les sols hydromorphes, These de l'Universite Aix Marseille III. Kass, A. Gavrieli, I. Yechieli, Y. Vengosh A.and Starinsky, A., 2005. The impact of freshwater and wastewater irrigation on the chemistry of shallow groundwater: a case study from the Israeli Coastal Aquifer, Journal of Hydrology, 300, 314-331.

Modified sedimentation-dispersion model for solids in a three-phase slurry column

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, D.N.; Ruether, J.A.; Shah, Y.T.

1986-03-01

Solids distribution data for a three-phase, batch-fluidized slurry bubble column (SBC) are presented, using air as the gas phase, pure liquids and solutions as the liquid phase, and glass beads and carborundum catalyst powder as the solid phase. Solids distribution data for the three-phase SBC operated in a continuous mode of operation are also presented, using nitrogen as the gas phase, water as the liquid phase, and glass beads as the solid phase. A new model to provide a reasonable approach to predict solids concentration distributions for systems containing polydispersed solids is presented. The model is a modification of standardmore » sedimentation-dispersion model published earlier. Empirical correlations for prediction of hindered settling velocity and solids dispersion coefficient for systems containing polydispersed solids are presented. A new method of evaluating critical gas velocity (CGV) from concentrations of the sample withdrawn at the same port of the SBC is presented. Also presented is a new mapping for CGV which separates the two regimes in the SBC, namely, incomplete fluidization and complete fluidization.« less

Effect of Different Treatment Technologies on the Fate of Antibiotic Resistance Genes and Class 1 Integrons when Residual Municipal Wastewater Solids are Applied to Soil.

PubMed

Burch, Tucker R; Sadowsky, Michael J; LaPara, Timothy M

2017-12-19

Residual wastewater solids are a significant reservoir of antibiotic resistance genes (ARGs). While treatment technologies can reduce ARG levels in residual wastewater solids, the effects of these technologies on ARGs in soil during subsequent land-application are unknown. In this study we investigated the use of numerous treatment technologies (air drying, aerobic digestion, mesophilic anaerobic digestion, thermophilic anaerobic digestion, pasteurization, and alkaline stabilization) on the fate of ARGs and class 1 integrons in wastewater solids-amended soil microcosms. Six ARGs [erm(B), qnrA, sul1, tet(A), tet(W), and tet(X)], the integrase gene of class 1 integrons (intI1), and 16S rRNA genes were quantified using quantitative polymerase chain reaction. The quantities of ARGs and intI1 decreased in all microcosms, but thermophilic anaerobic digestion, alkaline stabilization, and pasteurization led to the most extensive decay of ARGs and intI1, often to levels similar to that of the control microcosms to which no wastewater solids had been applied. In contrast, the rates by which ARGs and intI1 declined using the other treatment technologies were generally similar, typically varying by less than 2 fold. These results demonstrate that wastewater solids treatment technologies can be used to decrease the persistence of ARGs and intI1 during their subsequent application to soil.

Fate and aqueous transport of mercury in light of the Clean Air Mercury Rule for coal-fired electric power plants

NASA Astrophysics Data System (ADS)

Arzuman, Anry

Mercury is a hazardous air pollutant emitted to the atmosphere in large amounts. Mercury emissions from electric power generation sources were estimated to be 48 metric tons/year, constituting the single largest anthropogenic source of mercury in the U.S. Settled mercury species are highly toxic contaminants of the environment. The newly issued Federal Clean Air Mercury Rule requires that the electric power plants firing coal meet the new Maximum Achievable Mercury Control Technology limit by 2018. This signifies that all of the air-phase mercury will be concentrated in solid phase which, based on the current state of the Air Pollution Control Technology, will be fly ash. Fly ash is utilized by different industries including construction industry in concrete, its products, road bases, structural fills, monifills, for solidification, stabilization, etc. Since the increase in coal combustion in the U.S. (1.6 percent/year) is much higher than the fly ash demand, large amounts of fly ash containing mercury and other trace elements are expected to accumulate in the next decades. The amount of mercury transferred from one phase to another is not a linear function of coal combustion or ash production, depends on the future states of technology, and is unknown. The amount of aqueous mercury as a function of the future removal, mercury speciation, and coal and aquifer characteristics is also unknown. This paper makes a first attempt to relate mercury concentrations in coal, flue gas, fly ash, and fly ash leachate using a single algorithm. Mercury concentrations in all phases were examined and phase transformation algorithms were derived in a form suitable for probabilistic analyses. Such important parameters used in the transformation algorithms as Soil Cation Exchange Capacity for mercury, soil mercury selectivity sequence, mercury activity coefficient, mercury retardation factor, mercury species soil adsorption ratio, and mercury Freundlich soil adsorption isotherm coefficients were derived. Mercury air-phase removal efficiency was studied as a function of dominant mercury species vapor pressures, the amount of chlorine, sorbent injection rate and adsorption capacities, and process temperature and modifications. A mercury air phase removal algorithm was derived which defines the future removal efficiencies as a function of activated carbon injection rate. Mercury adsorption on soil was studied as a function of Mercury Mass Law incorporating the dominant aquatic mercury species, pH, chlorine and sulfur concentrations, and the amount of complexed hydroxyl groups. Aquatic mercury longitudinal plume delineation was studied using the Domenico and Robbins function. A Monte Carlo simulation was performed using random number series (5000) for all of the variables in the Domenico and Robbins and mercury retardation functions. The probability that the Maximum Contaminant Level for mercury will be exceeded was found to be equal approximately 1 percent of all soil-related fly ash applications.

Influence of the presence of PAHs and coal tar on naphthalene sorption in soils

NASA Astrophysics Data System (ADS)

Bayard, Rémy; Barna, Ligia; Mahjoub, Borhane; Gourdon, Rémy

2000-11-01

The mobility of the most water-soluble polynuclear aromatic hydrocarbons (PAHs) such as naphthalene in contaminated soils from manufactured gas plant (MGP) sites or other similar sites is influenced not only by the naturally occurring soil organic matter (SOM) but also, and in many cases mostly, by the nature and concentration of coal tar xenobiotic organic matter (XOM) and other PAH molecules present in the medium under various physical states. The objective of the present study was to quantify the effects of these factors using batch experiments, in order to simulate naphthalene transport in soil-tar-water systems using column experiments. Naphthalene sorption was studied in the presence of (i) solid coal tar particles, (ii) phenanthrene supplied as pure crystals, in the aqueous solution or already sorbed onto the soil, (iii) fluoranthene as pure crystals, and (iv) an aqueous solution of organic molecules extracted from a liquid tar. All experiments were conducted under abiotic conditions using short naphthalene/sorbent contact times of 24-60 h. Although these tests do not reflect true equilibrium conditions which usually take more time to establish, they were used to segregate relatively rapid sorption phenomena ("pseudo equilibrium") from slow sorption and other aging phenomena. For longer contact times, published data have shown that experimental biases due to progressive changes in the characteristics of the soil and the solution may drastically modify the affinity of the solutes for the soil. Slow diffusion in the microporosity and in dense organic phases may also become significant over the long term, along with some irreversible aging phenomena which have not been addressed in this work. Results showed that PAHs had no effect on naphthalene sorption when present in the aqueous solution or as pure crystals, due to their low solubility in water. Adsorbed phenanthrene was found to reduce naphthalene adsorption only when present at relatively high concentrations (about 120 mg/kg) in the soil. In contrast, experiments carried out with coal tar particles revealed a significant effect. Naphthalene sorption appeared to be proportional to the amount of coal tar added to the sand or soil, and a much higher affinity of naphthalene for XOM ( Koc above 2000 cm 3/g) than SOM ( Koc around 300 cm 3/g) was observed. Naphthalene transport in the columns of sand or soil spiked with coal tar particles was simulated very satisfactorily with a dual double-domain model. Around 90% of naphthalene retention by coal tar was found to occur within the organic phase, suggesting a phase partition process which may be explained by the amorphous nature of the XOM and its extreme affinity for naphthalene. For SOM, however, which is present as porous microaggregates of clay and humic substances, with less affinity for naphthalene, only 1/3 of naphthalene retention was found to occur within the organic phase, underlining the significant role of surface adsorption in the short term behavior of naphthalene in soil. For longer contact times, the model simulations proposed in the present study should be coupled to slow sorption, aging and biodegradation models to describe long-term behavior of naphthalene in soil-tar-water systems.

Assessing Metal Mobilization from Industrially Lead ...

EPA Pesticide Factsheets

A series of leaching and partitioning tests (Toxicity Characteristic Leaching Procedure (TCLP), Synthetic Precipitation Leaching Procedure (SPLP), Controlled Acidity Leaching Protocol (CALP), Acid Neutralization Capacity (ANC), and sequential extraction) were applied to three different soils to study potential mobility of metals into groundwater. Two of these soils were lead (Pb)-contaminated soils (Hotspot 1 and Hotspot 2) collected from an urban site associated with lead smelting and other industrial operations. The third sample (Stockpile) was soil affected by previous contamination in the area, removed from residential properties, stockpiled, and selected to be used as fill material in the studied site. The TCLP and CALP showed that Pb could be released from both hotspots, but were not released in the acidic rainfall extraction fluid of the SPLP. The sequential extraction showed that Pb in the hotspot soils was associated with the carbonate fraction, while As was associated with the Fe and Mn oxides. The stockpile released traces of Pb or As in the TCLP and CALP, but the ANC only released Pb under acidic conditions and the SPLP did not release Pb or As. Overall, the projected repository with Stockpile would not pose imminent danger to groundwater because, under the expected environmental conditions, Pb and As tend to remain in the solid phase. The objectives of this study were to determine if the stockpiled soil was suitable for the intended fill purpo

Method for the decontamination of soil containing solid organic explosives therein

DOEpatents

Radtke, Corey W.; Roberto, Francisco F.

2000-01-01

An efficient method for decontaminating soil containing organic explosives ("TNT" and others) in the form of solid portions or chunks which are not ordinarily subject to effective bacterial degradation. The contaminated soil is treated by delivering an organic solvent to the soil which is capable of dissolving the explosives. This process makes the explosives more bioavailable to natural bacteria in the soil which can decompose the explosives. An organic nutrient composition is also preferably added to facilitate decomposition and yield a compost product. After dissolution, the explosives are allowed to remain in the soil until they are decomposed by the bacteria. Decomposition occurs directly in the soil which avoids the need to remove both the explosives and the solvents (which either evaporate or are decomposed by the bacteria). Decomposition is directly facilitated by the solvent pre-treatment process described above which enables rapid bacterial remediation of the soil.

Influence of soil γ-irradiation and spiking on sorption of p,p'-DDE and soil organic matter chemistry.

PubMed

Škulcová, Lucia; Scherr, Kerstin E; Chrást, Lukáš; Hofman, Jakub; Bielská, Lucie

2018-07-15

The fate of organic chemicals and their metabolites in soils is often investigated in model matrices having undergone various pre-treatment steps that may qualitatively or quantitatively interfere with the results. Presently, effects associated with soil sterilization by γ-irradiation and soil spiking using an organic solvent were studied in one freshly spiked soil (sterilization prior to contamination) and its field-contaminated (sterilization after contamination) counterpart for the model organic compound 1,1-Dichloro-2,2-bis(4-chlorophenyl)ethene (p,p'-DDE). Changes in the sorption and potential bioavailability of spiked and native p,p'-DDE were measured by supercritical fluid extraction (SFE), XAD-assisted extraction (XAD), and solid-phase microextraction (SPME) and linked to qualitative changes in soil organic matter (SOM) chemistry measured by diffuse reflectance infrared Fourier-transform (DRIFT) spectroscopy. Reduced sorption of p,p´-DDE detected with XAD and SPME was associated more clearly with spiking than with sterilization, but SFE showed a negligible impact. Spiking resulted in an increase of the DRIFT-derived hydrophobicity index, but irradiation did not. Spectral peak height ratio descriptors indicated increasing hydrophobicity and hydrophilicity in pristine soil following sterilization, and a greater reduction of hydrophobic over hydrophilic groups as a consequence of spiking. In parallel, reduced sorption of p,p´-DDE upon spiking was observed. Based on the present samples, γ-irradiation appears to alter soil sorptive properties to a lesser extent when compared to common laboratory processes such as spiking with organic solvents. Copyright © 2018. Published by Elsevier Inc.

Gone or just out of sight? The apparent disappearance of aromatic litter components in soils

NASA Astrophysics Data System (ADS)

Klotzbücher, Thimo; Kalbitz, Karsten; Cerli, Chiara; Hernes, Peter J.; Kaiser, Klaus

2016-07-01

Uncertainties concerning stabilization of organic compounds in soil limit our basic understanding on soil organic matter (SOM) formation and our ability to model and manage effects of global change on SOM stocks. One controversially debated aspect is the contribution of aromatic litter components, such as lignin and tannins, to stable SOM forms. In the present opinion paper, we summarize and discuss the inconsistencies and propose research options to clear them. Lignin degradation takes place stepwise, starting with (i) depolymerization and followed by (ii) transformation of the water-soluble depolymerization products. The long-term fate of the depolymerization products and other soluble aromatics, e.g., tannins, in the mineral soils is still a mystery. Research on dissolved organic matter (DOM) composition and fluxes indicates dissolved aromatics are important precursors of stable SOM attached to mineral surfaces and persist in soils for centuries to millennia. Evidence comes from flux analyses in soil profiles, biodegradation assays, and sorption experiments. In contrast, studies on composition of mineral-associated SOM indicate the prevalence of non-aromatic microbial-derived compounds. Other studies suggest the turnover of lignin in soil can be faster than the turnover of bulk SOM. Mechanisms that can explain the apparent fast disappearance of lignin in mineral soils are, however, not yet identified. The contradictions might be explained by analytical problems. Commonly used methods probably detect only a fraction of the aromatics stored in the mineral soil. Careful data interpretation, critical assessment of analytical limitations, and combined studies on DOM and solid-phase SOM could thus be ways to unveil the issues.

Gone or just out of sight? The apparent disappearance of aromatic litter components in soils

NASA Astrophysics Data System (ADS)

Klotzbücher, Thimo; Kalbitz, Karsten; Cerli, Chiara; Hernes, Peter; Kaiser, Klaus

2016-04-01

Uncertainties concerning stabilization of organic compounds in soil limit our basic understanding on soil organic matter (SOM) formation and our ability to model and manage effects of global change on SOM stocks. One controversially debated aspect is the contribution of aromatic litter components, such as lignin and tannins, to stable SOM forms. Here we summarize and discuss the inconsistencies and propose research options to clear them. Lignin degradation takes place step-wise, starting with (i) depolymerisation, followed by (ii) transformation of the water-soluble depolymerization products. The long-term fate of the depolymerization products and other soluble aromatics, e.g., tannins, in the mineral soils is still a mystery. Research on dissolved organic matter (DOM) composition and fluxes indicates dissolved aromatics are important precursors of stable SOM attached to mineral surfaces and persist in soils for centuries to millennia. Evidence comes from flux analyses in soil profiles, biodegradation assays, and sorption experiments. In contrast, studies on composition of mineral-associated SOM indicate the prevalence of non-aromatic microbial-derived compounds. Other studies suggest the turnover of lignin in soil can be faster than the turnover of bulk SOM. Mechanisms that can explain the apparent fast disappearance of lignin in mineral soils are, however, not yet identified. The contradictions might be explained by analytical problems. Commonly used methods probably detect only a fraction of the aromatics stored in the mineral soil. Careful data interpretation, critical assessment of analytical limitations, and combined studies on DOM and solid-phase SOM could thus be ways to unveil the issues.

Long-term contamination in a recovered area affected by a mining spill.

PubMed

Martín Peinado, F J; Romero-Freire, A; García Fernández, I; Sierra Aragón, M; Ortiz-Bernad, I; Simón Torres, M

2015-05-01

Soil pollution from the spill of Aznalcóllar mine (S Spain) was monitored by analysing polluted soils in 1998, 1999, and 2004. Following the methodology used in previous studies, in 2013 we conducted a new sampling and analysis of the soils affected by the spill and the data were compared with those of 2004. The results confirm that the pH tended to rise and concentration of pollutants tended to diminish over time. In 2013, the total concentration of pollutants was within the normal range for uncontaminated soils and close to the background concentration of the soils prior to the spill; while the soluble concentration of pollutants was clearly below the toxic level. These results indicate that remediation measures implemented have been effective. However, the removal of tailings (first remediation measure applied) was deficient and in many places the tailings were mixed with the soil. The high concentration of sulphides and metal(loid)s in the tailings gave rise to spots with very acidic and highly polluted soils devoid of vegetation. In 2013, fifteen years after the spill, these spots of bare soils remain a major source of pollution from which pollutants are scattered through the solid and liquid phases of runoff water, requiring action to immobilize pollutants and encourage the restoration of vegetation on these soils. In this type of pollution in a Mediterranean environment, the complete removal of tailings is more important than the speed at which they are removed. Copyright © 2015 Elsevier B.V. All rights reserved.

Profiling of soil volatile organic compounds after long-term application of inorganic, organic and organic-inorganic mixed fertilizers and their effect on plant growth.

PubMed

Raza, Waseem; Mei, Xinlan; Wei, Zhong; Ling, Ning; Yuan, Jun; Wang, Jichen; Huang, Qiwei; Shen, Qirong

2017-12-31

The complexity of soil processes involved in the production, consumption and accumulation of volatile organic compounds (VOCs) makes hard to access the overall dynamics of VOCs in the soil. In this study, the field soil, applied with inorganic (CF), organic (OF) and inorganic-organic mixed (CFOF) fertilizers for ten years was evaluated for the emission of VOCs at different temperature and moisture levels. We identified 30-50 soil emitted VOCs representing the most common soil VOCs groups by using the solid-phase microextraction (SPME) fiber and gas chromatography-mass spectroscopy. The highest total emission of VOCs was found in OF treatment, but it was non-significantly different with CF treatment. The emission of VOCs was significantly increased with the decrease in moisture contents and increase in the temperature of the soil. Among different fertilizer treatments, the emission of VOCs was significantly higher in OF treatment at 5% moisture, and in CF and OF treatments at 35°C. Further, the VOCs emitted from soil treated with CFOF showed the highest increase in plant growth while CF and OF treatments showed similar results. The VOCs were also extracted from the soil using methanol to better understand the dynamics of VOCs. The abundance of VOCs extracted from the soil was 44-61%, while the richness was 65-70% higher than the VOCs emitted from the soil in different treatments. Taken together the results of emitted and extracted VOCs from the soil, we conclude that the fertilizers are able to discriminate among the VOC patterns of soil. In addition, most of the VOCs are retained in the soil and the emission of VOCs from soil depends on the type of VOCs, soil properties and environmental conditions; however, more research is required to find out better soil VOCs analysis methods. Copyright © 2017. Published by Elsevier B.V.

Solid state phase change materials for thermal energy storage in passive solar heated buildings

NASA Astrophysics Data System (ADS)

Benson, D. K.; Christensen, C.

1983-11-01

A set of solid state phase change materials was evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol, pentaglycerine and neopentyl glycol. Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature within the range from less than 25 deg to 188 deg. Thermophysical properties such as thermal conductivity, density and volumetric expansion were measured. Computer simulations were used to predict the performance of various Trombe wall designs incorporating solid state phase change materials. Optimum performance was found to be sensitive to the choice of phase change temperatures and to the thermal conductivity of the phase change material. A molecular mechanism of the solid state phase transition is proposed and supported by infrared spectroscopic evidence.

Experimental study of the dynamics of penetration of a solid body into a soil medium

NASA Astrophysics Data System (ADS)

Balandin, Vl. V.; Balandin, Vl. Vl.; Bragov, A. M.; Kotov, V. L.

2016-06-01

An experimental system is developed to determine the main parameters of the impact and penetration of a solid deformable body into a soft soil medium. This system is based on the technique of an inverse experiment with a measuring rod and the technique of a direct experiment with photo recording and the application of a shadow picture of the interaction of a striker with a soil target. To verify these techniques, the collision of a solid body with soil is studied by a numerical calculation and the time intervals in which the change of the resistance force is proportional to the penetration velocity squared are determined. The penetration resistance coefficients determined in direct and inverse experiments are shown to agree with each other in the collision velocity range 80-400 m/s, which supports the validity of the techniques and the reliability of measuring the total load.

Glufosinate ammonium clean-up procedure from water samples using SPE

NASA Astrophysics Data System (ADS)

Tayeb M., A.; Ismail B., S.; Mardiana-Jansar, K.; Ta, Goh Choo; Agustar, Hani Kartini

2015-09-01

For the determination of glufosinate ammonium residue in soil and water samples, different solid phase extraction (SPE) sorbent efficiency was studied. Four different SPE sorbents i.e.: CROMABOND PS-H+, CROMABOND PS-OH-, ISOLUTE ENV+, Water Sep-Pak and OASIS HLB were used. Sample clean-up performance was evaluated using high performance liquid chromatography (Agilent 1220 infinity LC) with fluorescence detector. Detection of FMO-derivatives was done at λ ex = 260 nm and λ em= 310 nm. OASIS HLB column was the most suitable for the clean-up in view of the overall feasibility of the analysis.

Structural analysis of geochemical samples by solid-state nuclear magnetic resonance spectrometry. Role of paramagnetic material

USGS Publications Warehouse

Vassallo, A.M.; Wilson, M.A.; Collin, P.J.; Oades, J.M.; Waters, A.G.; Malcolm, R.L.

1987-01-01

An examination of coals, coal tars, a fulvic acid, and soil fractions by solid-state 13C NMR spectrometry has demonstrated widely differing behavior regarding quantitative representation in the spectrum. Spin counting experiments on coal tars and the fulvic acid show that almost all the sample carbon is observed in both solution and solid-state NMR spectra. Similar experiments on two coals (a lignite and a bituminous coal) show that most (70-97%) of the carbon is observed; however, when the lignite is ion exchanged with 3% (w/w) Fe3+, the fraction of carbon observed drops to below 10%. In additional experiments signal intensity from soil samples is enhanced by a simple dithionite treatment. This is illustrated by 13C, 27Al, and 29Si solid-state NMR experiments on soil fractions. ?? 1987 American Chemical Society.

Mass balance evaluation of polybrominated diphenyl ethers in landfill leachate and potential for transfer from e-waste.

PubMed

Danon-Schaffer, Monica N; Mahecha-Botero, Andrés; Grace, John R; Ikonomou, Michael

2013-09-01

Previous research on brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs) has largely focussed on their concentrations in the environment and their adverse effects on human health. This paper explores their transfer from waste streams to water and soil. A comprehensive mass balance model is developed to track polybrominated diphenyl ethers (PBDEs), originating from e-waste and non-e-waste solids leaching from a landfill. Stepwise debromination is assumed to occur in three sub-systems (e-waste, aqueous leachate phase, and non-e-waste solids). Analysis of landfill samples and laboratory results from a solid-liquid contacting chamber are used to estimate model parameters to simulate an urban landfill system, for past and future scenarios. Sensitivity tests to key model parameters were conducted. Lower BDEs require more time to disappear than high-molecular weight PBDEs, since debromination takes place in a stepwise manner, according to the simplified reaction scheme. Interphase mass transfer causes the decay pattern to be similar in all three sub-systems. The aqueous phase is predicted to be the first sub-system to eliminate PBDEs if their input to the landfill were to be stopped. The non-e-waste solids would be next, followed by the e-waste sub-system. The model shows that mass transfer is not rate-limiting, but the evolution over time depends on the kinetic degradation parameters. Experimental scatter makes model testing difficult. Nevertheless, the model provides qualitative understanding of the influence of key variables. Copyright © 2013 Elsevier B.V. All rights reserved.

Mechanisms controlling lateral and vertical porewater migration of depleted uranium (DU) at two UK weapons testing sites.

PubMed

Graham, Margaret C; Oliver, Ian W; MacKenzie, Angus B; Ellam, Robert M; Farmer, John G

2011-04-15

Uranium associations with colloidal and truly dissolved soil porewater components from two Ministry of Defence Firing Ranges in the UK were investigated. Porewater samples from 2-cm depth intervals for three soil cores from each of the Dundrennan and Eskmeals ranges were fractionated using centrifugal ultrafiltration (UF) and gel electrophoresis (GE). Soil porewaters from a transect running downslope from the Dundrennan firing area towards a stream (Dunrod Burn) were examined similarly. Uranium concentrations and isotopic composition were determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Multi-Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS), respectively. The soils at Dundrennan were Fe- and Al-rich clay-loam soils whilst at Eskmeals, they were Fe- and Al-poor sandy soils; both, however, had similar organic matter contents due to the presence of a near-surface peaty layer at Eskmeals. These compositional features influenced the porewater composition and indeed the associations of U (and DU). In general, at Dundrennan, U was split between large (100kDa-0.2μm) and small (3-30kDa) organic colloids whilst at Eskmeals, U was mainly in the small colloidal and truly dissolved fractions. Especially below 10cm depth, association with large Fe/Al/organic colloids was considered to be a precursor to the removal of U from the Dundrennan porewaters to the solid phase. In contrast, the association of U with small organic colloids was largely responsible for inhibiting attenuation in the Eskmeals soils. Lateral migration of U (and DU) through near-surface Dundrennan soils will involve both large and small colloids but, at depth, transport of the smaller amounts of U remaining in the porewaters may involve large colloids only. For one of the Dundrennan cores the importance of redox-related processes for the re-mobilisation of DU was also indicated as Mn(IV) reduction resulted in the release of both Mn(II) and U(VI) into the truly dissolved phase. Copyright © 2011 Elsevier B.V. All rights reserved.

A novel method to measure isotopic labeled gas-phase nitrous acid (HO15NO) in biogeochemical studies

NASA Astrophysics Data System (ADS)

Wu, Dianming; Kampf, Christopher; Pöschl, Ulrich; Oswald, Robert; Cui, Junfang; Ermel, Michael; Hu, Chunsheng; Trebs, Ivonne; Sörgel, Matthias

2014-05-01

We developed a new method (gas-phase stripping-derivatization coupled to LC-MS) to measure the 15N atom percent excess (APE) of HONO in the gas-phase. Gaseous HONO is quantitatively collected and transferred to an azo dye by the well-known Griess reaction in the Long Path Absorption Photometer (LOPAP). The reaction solutions containing the dye are collected at the outflow of the LOPAP, purified by solid-phase extraction and analyzed using high performance liquid chromatography coupled to mass spectrometry (HPLC-MS). The unlabeled azo dye (C18H19O2N5S) with a monoisotopic molecular mass of 369.41 g mol-1 can be detected as its protonated molecular ion ([M+H+], M) by HPLC-MS at a retention time of 2.8 min. Due to the natural isotope distribution M + 0, M + 1, M + 2, and M + 3 ions were considered for the calculation of the 15N APE. The optimal working range was found to be between 20 and 50% for the 15N/14N ratio. The optimum pH and solvents for extraction by SPE and potential interferences are discussed. The method has been applied for the measurement of HO15NO emissions from soil in a dynamic chamber with and without spiking 15N labeled urea. Our results confirm biogenic HONO emissions from soil as HO15NO was measured after addition of 15N urea.

Arsenic removal from contaminated brackish sea water by sorption onto Al hydroxides and Fe phases mobilized by land-use.

PubMed

Yu, Changxun; Peltola, Pasi; Nystrand, Miriam I; Virtasalo, Joonas J; Österholm, Peter; Ojala, Antti E K; Hogmalm, Johan K; Åström, Mats E

2016-01-15

This study examines the spatial and temporal distribution patterns of arsenic (As) in solid and aqueous materials along the mixing zone of an estuary, located in the south-eastern part of the Bothnian Bay and fed by a creek running through an acid sulfate (AS) soil landscape. The concentrations of As in solution form (<1 kDa) increase steadily from the creek mouth to the outer estuary, suggesting that inflowing seawater, rather than AS soil, is the major As source in the estuary. In sediments at the outer estuary, As was accumulated and diagenetically cycled in the surficial layers, as throughout much of the Bothnian Bay. In contrast, in sediments in the inner estuary, As concentrations and accumulation rates showed systematical peaks at greater depths. These peaks were overall consistent with the temporal trend of past As discharges from the Rönnskär smelter and the accompanied As concentrations in past sea-water of the Bothnian Bay, pointing to a connection between the historical smelter activities and the sediment-bound As in the inner estuary. However, the concentrations and accumulation rates of As peaked at depths where the smelter activities had already declined, but a large increase in the deposition of Al hydroxides and Fe phases occurred in response to intensified land-use in the mid 1960's and early 1970's. This correspondence suggests that, apart from the inflowing As-contaminated seawater, capture by Al hydroxides, Fe hydroxides and Fe-organic complexes is another important factor for As deposition in the inner estuary. After accumulating in the sediment, the solid-phase As was partly remobilized, as reflected by increased pore-water As concentrations, a process favored by As(V) reduction and high concentrations of dissolved organic matter. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular aspects of aromatic C additions to soils: Implications of char quality for ecosystem functionality

NASA Astrophysics Data System (ADS)

Keiluweit, M.; Nico, P. S.; Johnson, M. G.; Kleber, M.

2009-12-01

Solid residues of incomplete combustion (biochar or char) are continuously being added to soils due to natural vegetation fires in many ecosystems. However, new strategies for carbon sequestration in soils are likely to include the active addition of biochar to soils. Since biochar is a highly aromatic organic material such additions will modify the native molecular structure of soil organic matter and thus alter interactions with the global atmosphere and hydrosphere. Here we present a molecular level assessment of the physical organization and chemical complexity of biomass-derived chars and, specifically, that of aromatic carbon in char structures. Differences among wood and grass charred at temperatures from 100 to 700°C are investigated. BET-N2 surface area, X-ray diffraction (XRD), synchrotron-based Near-edge X-ray Absorption Fine Structure (NEXAFS) and Fourier transform infrared (FT-IR) spectroscopy results demonstrate how the two plant precursor materials undergo analogous, but quantitatively different physical-chemical transitions as charring intensity increases. These changes suggest the existence of four distinct physical and chemical categories of char. We find that each category of char consists of a unique mixture of chemical phases and physical states: (i) in transition chars the crystalline character of the precursor materials is preserved, (ii) in amorphous chars the heat-altered molecules and incipient aromatic polycondensates are randomly mixed, (iii) composite chars consist of poorly ordered graphene stacks embedded in amorphous phases, and (iv) turbostratic chars are dominated by turbostratic (disordered) graphitic crystallites. There is wide variation in both the chemical and the physical nature of aromatic carbon among these char categories. In this presentation we will point out how molecular variations among the aromatic components of the different char categories translate into differences in their ability to: (i) persist in the environment, (ii) function as environmental sorbents, and (iii) to enable the soil to provide environmental services.

Quaternary ammonium-functionalized silica sorbents for the solid-phase extraction of aromatic amines under normal phase conditions.

PubMed

Vidal, Lorena; Robin, Orlane; Parshintsev, Jevgeni; Mikkola, Jyri-Pekka; Riekkola, Marja-Liisa

2013-04-12

Quaternary ammonium-functionalized silica materials were synthesized and applied for solid-phase extraction (SPE) of aromatic amines, which are classified as priority pollutants by US Environmental Protection Agency. Hexamethylenetetramine used for silica surface modification for the first time was employed as SPE sorbent under normal phase conditions. Hexaminium-functionalized silica demonstrated excellent extraction efficiencies for o-toluidine, 4-ethylaniline and quinoline (recoveries 101-107%), while for N,N-dimethylaniline and N-isopropylaniline recoveries were from low to moderate (14-46%). In addition, the suitability of 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica as SPE sorbent was tested under normal phase conditions. The recoveries achieved for the five aromatic amines ranged from 89 to 99%. The stability of the sorbent was evaluated during and after 150 extractions. Coefficients of variation between 4.5 and 10.2% proved a high stability of the synthesized sorbent. Elution was carried out using acetonitrile in the case of hexaminium-functionalized silica and water for 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent. After the extraction the analytes were separated and detected by liquid chromatography ultraviolet detection (LC-UV). The retention mechanism of the materials was primarily based on polar hydrogen bonding and π-π interactions. Comparison made with activated silica proved the quaternary ammonium-functionalized materials to offer different selectivity and better extraction efficiencies for aromatic amines. Finally, 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent was successfully tested for the extraction of wastewater and soil samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Measuring air-water interfacial area for soils using the mass balance surfactant-tracer method.

PubMed

Araujo, Juliana B; Mainhagu, Jon; Brusseau, Mark L

2015-09-01

There are several methods for conducting interfacial partitioning tracer tests to measure air-water interfacial area in porous media. One such approach is the mass balance surfactant tracer method. An advantage of the mass-balance method compared to other tracer-based methods is that a single test can produce multiple interfacial area measurements over a wide range of water saturations. The mass-balance method has been used to date only for glass beads or treated quartz sand. The purpose of this research is to investigate the effectiveness and implementability of the mass-balance method for application to more complex porous media. The results indicate that interfacial areas measured with the mass-balance method are consistent with values obtained with the miscible-displacement method. This includes results for a soil, for which solid-phase adsorption was a significant component of total tracer retention. Copyright © 2015 Elsevier Ltd. All rights reserved.

Pedologic Factors Affecting Virgin Olive Oil Quality of "Chemlali" Olive Trees (Olea europaea L.).

PubMed

Rached, Mouna Ben; Galaverna, Gianni; Cirlini, Martina; Boujneh, Dalenda; Zarrouk, Mokhtar; Guerfel, Mokhtar

2017-08-01

The aim of this study examined the characterization of extra virgin olive oil samples from the main cultivar Chemlali, grown in five olive orchards with different soil type (Sandy, Clay, Stony, Brown, Limestone and Gypsum). Volatile compounds were studied using headspace-solid phase micro-extraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) technics. Moreover, the sterol profile was established using gas chromatography-mass spectrometry. 35 different volatile compounds were identified: alcohols, esters, aldehydes, ketones and hydrocarbons. The chemical composition of the volatile fraction was characterized by the preeminence of 2-hexenal (32.75%) and 1-hexanol (31.88%). Three sterols were identified and characterized. For all olive oil samples, ß-sitosterol (302.25 mg/kg) was the most abundant sterol. Interestingly, our results showed significant qualitative and quantitative differences in the levels of the volatile compounds and sterols from oils obtained from olive trees grown in different soil type.

Does Diffusion Sequester Heavy Metals in Old Contamination Soils?

NASA Astrophysics Data System (ADS)

Ma, J.; Jennings, A. A.

2002-12-01

Old soil contamination refers to soil contamination that has aged over a long period of time. For example, at some brownfields, the soil heavy metal contamination can be one hundred or more years old. When contamination is young, the heavy metals are bound relatively weakly to the soil. However, the speciation and/or mechanisms of association evolve with aging into much more stable forms. It also appears that the metals migrate deeper into the bulk soil matrix where they are less available to participate in surface-related phenomena. Previous research showed elevated heavy metal extraction result after the soil was pulverized, with all other experiment conditions remaining unchanged. This indicates the presence of sequestered heavy metal contamination within the large soil particles (aggregate). The mechanisms of sequestering are uncertain, but diffusion appears to be a major factor. There are two possible pathways of diffusion that can account for heavy metal sequestering: solid-state diffusion through the bulk aggregate or liquid-phase diffusion through micro-pores within the aggregate structure. The second diffusion mechanism can be coupled with sorption (or other surface-related phenomena) on the pore walls. The remediation of sequestered heavy metals is also impacted by diffusion. Grinding a soil significantly reduces its average particle size. This exposes more of its internal bulk volume to extraction and results in much shorter diffusion pathway for the sequestered heavy metals to be released. Evidence has illustrated that this both improves remediation efficiency and provides a method by which the degree of sequestering can be quantified. This paper will present the results of ongoing research that is developing methods to identify the mechanisms of, quantify the magnitude of and determine the relative importance of (i.e. risk analysis) heavy metals sequestered in old contamination soils.

Calculating carbon mass balance from unsaturated soil columns treated with CaSO₄₋minerals: test of soil carbon sequestration.

PubMed

Han, Young-Soo; Tokunaga, Tetsu K

2014-12-01

Renewed interest in managing C balance in soils is motivated by increasing atmospheric concentrations of CO2 and consequent climate change. Here, experiments were conducted in soil columns to determine C mass balances with and without addition of CaSO4-minerals (anhydrite and gypsum), which were hypothesized to promote soil organic carbon (SOC) retention and soil inorganic carbon (SIC) precipitation as calcite under slightly alkaline conditions. Changes in C contents in three phases (gas, liquid and solid) were measured in unsaturated soil columns tested for one year and comprehensive C mass balances were determined. The tested soil columns had no C inputs, and only C utilization by microbial activity and C transformations were assumed in the C chemistry. The measurements showed that changes in C inventories occurred through two processes, SOC loss and SIC gain. However, the measured SOC losses in the treated columns were lower than their corresponding control columns, indicating that the amendments promoted SOC retention. The SOC losses resulted mostly from microbial respiration and loss of CO2 to the atmosphere rather than from chemical leaching. Microbial oxidation of SOC appears to have been suppressed by increased Ca(2+) and SO4(2)(-) from dissolution of CaSO4 minerals. For the conditions tested, SIC accumulation per m(2) soil area under CaSO4-treatment ranged from 130 to 260 g C m(-1) infiltrated water (20-120 g C m(-1) infiltrated water as net C benefit). These results demonstrate the potential for increasing C sequestration in slightly alkaline soils via CaSO4-treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Relating environmental availability to bioavailability: soil-type-dependent metal accumulation in the oligochaete Eisenia andrei.

PubMed

Peijnenburg, W J; Baerselman, R; de Groot, A C; Jager, T; Posthuma, L; Van Veen, R P

1999-11-01

Body residues are often better estimates of the amount of a chemical at the sites of toxic action in an organism than ambient soil concentrations, because bioavailability differences among soils are explicitly taken into account in considerations of body residues. Often, however, insufficient attention is paid to the rate and extent at which tissue concentrations respond to soil concentrations and soil characteristics. In this contribution the impact of soil characteristics on the environmental bioavailability of heavy metals for the oligochaete worm Eisenia andrei is reported. Uptake of As, Cd, Cr, Cu, Ni, Pb, and Zn in 20 Dutch field soils and in OECD artificial soil was quantified as a function of time. Internal metal concentrations varied less than the corresponding external levels. Metal uptake and elimination were both metal- and species-dependent. Worms typically attained steady-state concentrations rapidly for Cr, Cu, Ni, and Zn. Internal concentrations similar to those in the cultivation medium, linearly increasing body concentrations, or steady-state internal concentrations well above those in the cultivation medium were found for As, Cd, and Pb. Multivariate expressions were derived to describe uptake rate constants, steady-state concentrations, and bioaccumulation factors as a function of soil characteristics. Soil acidity is the most important solid-phase characteristic modulating the availability of As, Cd, and Pb. Although additional semimechanistic calculations yielded evidence of pore-water-related uptake of Cd and Pb modulated by competition between H(+) and metal ions at the active sites of the membranes, the findings for Cr, Cu, Ni, and Zn point to additional influences, among which is probably regulation. Copyright 1999 Academic Press.

Soils in our big back yard: characterizing the state, vulnerabilities, and opportunities for detecting changes in soil carbon storage

NASA Astrophysics Data System (ADS)

Harden, Jennifer W.; Loiesel, Julie; Ryals, Rebecca; Lawrence, Corey; Blankinship, Joseph; Phillips, Claire; Bond-Lamberty, Ben; Todd-Brown, Katherine; Vargas, Rodrigo; Hugelius, Gustaf; Nave, Luke; Malhotra, Avni; Silver, Whendee; Sanderman, Jon

2017-04-01

A number of diverse approaches and sciences can contribute to a robust understanding of the I. state, II. vulnerabilities, and III. opportunities for soil carbon in context of its potential contributions to the atmospheric C budget. Soil state refers to the current C stock of a given site, region, or ecosystem/landuse type. Soil vulnerabilities refers to the forms and bioreactivity of C stocks, which determine how soil C might respond to climate, disturbance, and landuse perturbations. Opportunities refer to the potential for soils in their current state to increase capacity for and rate of C storage under future conditions, thereby impacting atmospheric C budgets. In order to capture the state, vulnerability, and opportunities for soil C, a robust C accounting scheme must include at least three science needs: (1) a user-friendly and dynamic database with transparent, shared coding in which data layers of solid, liquid, and gaseous phases share relational metadata and allow for changes over time (2) a framework to characterize the capacity and reactivity of different soil types based on climate, historic, and landscape factors (3) a framework to characterize landuse practices and their impact on physical state, capacity/reactivity, and potential for C change. In order to transfer our science information to practicable implementations for land policies, societal and social needs must also include: (1) metrics for landowners and policy experts to recognize conditions of vulnerability or opportunity (2)communication schemes for accessing salient outcomes of the science. Importantly, there stands an opportunity for contributions of data, model code, and conceptual frameworks in which scientists, educators, and decision-makers can become citizens of a shared, scrutinized database that contributes to a dynamic, improved understanding of our soil system.

Experimental study on microstructure characters of foamed lightweight soil

NASA Astrophysics Data System (ADS)

Qiu, Youqiang; Li, Yongliang; Li, Meixia; Liu, Yaofu; Zhang, Liujun

2018-01-01

In order to verify the microstructure of foamed lightweight soil and its characters of compressive strength, four foamed lightweight soil samples with different water-soild ratio were selected and the microstructure characters of these samples were scanned by electron microscope. At the same time, the characters of compressive strength of foamed lightweight soil were analyzed from the microstructure. The study results show that the water-soild ratio has a prominent effect on the microstructure and compressive strength of foamed lightweight soil, with the decrease of water-solid ratio, the amount and the perforation of pores would be reduced significantly, thus eventually forming a denser and fuller interior structure. Besides, the denser microstructure and solider pore-pore wall is benefit to greatly increase mechanical intensity of foamed lightweight soil. In addition, there are very few acicular ettringite crystals in the interior of foamed lightweight soil, its number is also reduced with the decrease in water-soild ratio.

The Impact of Solid Surface Features on Fluid-Fluid Interface Configuration

NASA Astrophysics Data System (ADS)

Araujo, J. B.; Brusseau, M. L. L.

2017-12-01

Pore-scale fluid processes in geological media are critical for a broad range of applications such as radioactive waste disposal, carbon sequestration, soil moisture distribution, subsurface pollution, land stability, and oil and gas recovery. The continued improvement of high-resolution image acquisition and processing have provided a means to test the usefulness of theoretical models developed to simulate pore-scale fluid processes, through the direct quantification of interfaces. High-resolution synchrotron X-ray microtomography is used in combination with advanced visualization tools to characterize fluid distributions in natural geologic media. The studies revealed the presence of fluid-fluid interface associated with macroscopic features on the surfaces of the solids such as pits and crevices. These features and respective fluid interfaces, which are not included in current theoretical or computational models, may have a significant impact on accurate simulation and understanding of multi-phase flow, energy, heat and mass transfer processes.

Retention of 14C-labeled multiwall carbon nanotubes by humic acid and polymers: Roles of macromolecule properties

PubMed Central

Zhao, Qing; Petersen, Elijah J.; Cornelis, Geert; Wang, Xilong; Guo, Xiaoying; Tao, Shu; Xing, Baoshan

2016-01-01

Developing methods to measure interactions of carbon nanotubes (CNTs) with soils and sediments and understanding the impact of soil and sediment properties on CNT deposition are essential for assessing CNT environmental risks. In this study, we utilized functionalized carbon-14 labeled nanotubes to systematically investigate retention of multiwall CNTs (MWCNTs) by 3 humic acids, 3 natural biopolymers, and 10 model solid-phase polymers, collectively termed macromolecules. Surface properties, rather than bulk properties of macromolecules, greatly influenced MWCNT retention. As shown via multiple linear regression analysis and path analysis, aromaticity and surface polarity were the two most positive factors for retention, suggesting retention was regulated by π-π stacking and hydrogen bonding interactions. Moreover, MWCNT deposition was irreversible. These observations may explain the high retention of MWCNT in natural soils. Moreover, our findings on the relative contribution of each macromolecule property on CNT retention provide information on macromolecule selection for removal of MWCNTs from wastewater and provide a method for measuring CNT interactions with organic macromolecules. PMID:27458320

Optimized demineralization technique for the measurement of stable isotope ratios of nonexchangeable H in soil organic matter.

PubMed

Ruppenthal, Marc; Oelmann, Yvonne; Wilcke, Wolfgang

2013-01-15

To make use of the isotope ratio of nonexchangeable hydrogen (δ(2)H(n (nonexchangeable))) of bulk soil organic matter (SOM), the mineral matrix (containing structural water of clay minerals) must be separated from SOM and samples need to be analyzed after H isotope equilibration. We present a novel technique for demineralization of soil samples with HF and dilute HCl and recovery of the SOM fraction solubilized in the HF demineralization solution via solid-phase extraction. Compared with existing techniques, organic C (C(org)) and organic N (N(org)) recovery of demineralized SOM concentrates was significantly increased (C(org) recovery using existing techniques vs new demineralization method: 58% vs 78%; N(org) recovery: 60% vs 78%). Chemicals used for the demineralization treatment did not affect δ(2)H(n) values as revealed by spiking with deuterated water. The new demineralization method minimized organic matter losses and thus artificial H isotope fractionation, opening up the opportunity to use δ(2)H(n) analyses of SOM as a new tool in paleoclimatology or geospatial forensics.

Multi-residue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry: optimisation and matrix effects reduction by quick, easy, cheap, effective, rugged and safe extraction.

PubMed

Bourdat-Deschamps, Marjolaine; Leang, Sokha; Bernet, Nathalie; Daudin, Jean-Jacques; Nélieu, Sylvie

2014-07-04

The aim of this study was to develop and optimise an analytical method for the quantification of a bactericide and 13 pharmaceutical products, including 8 antibiotics (fluoroquinolones, tetracyclines, sulfonamides, macrolide), in various aqueous environmental samples: soil water and aqueous fractions of pig slurry, digested pig slurry and sewage sludge. The analysis was performed by online solid-phase extraction coupled to ultra-high performance liquid chromatography with tandem mass spectrometry (online SPE-UHPLC-MS-MS). The main challenge was to minimize the matrix effects observed in mass spectrometry, mostly due to ion suppression. They depended on the dissolved organic carbon (DOC) content and its origin, and ranged between -22% and +20% and between -38% and -93% of the signal obtained without matrix, in soil water and slurry supernatant, respectively. The very variable levels of these matrix effects suggested DOC content cut-offs above which sample purification was required. These cut-offs depended on compounds, with concentrations ranging from 30 to 290mgC/L for antibiotics (except tylosine) up to 600-6400mgC/L for the most apolar compounds. A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure was therefore optimised using an experimental design methodology, in order to purify samples with high DOC contents. Its performance led to a compromise, allowing fluoroquinolone and tetracycline analysis. The QuEChERS extraction salts consisted therefore of sodium acetate, sodium sulfate instead of magnesium sulfate, and sodium ethylenediaminetetraacetate (EDTA) as a ligand of divalent cations. The modified QuEChERS procedure employed for the extraction of pharmaceuticals in slurry and digested slurry liquid phases reduced the matrix effects for almost all the compounds, with extraction recoveries generally above 75%. The performance characteristics of the method were evaluated in terms of linearity, intra-day and inter-day precision, accuracy and limits of quantification, which reached concentration ranges of 5-270ng/L in soil water and sludge supernatant, and 31-2400ng/L in slurry and digested slurry supernatants, depending on the compounds. The new method was then successfully applied for the determination of the target compounds in environmental samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Interactions of organic contaminants with mineral-adsorbed surfactants

USGS Publications Warehouse

Zhu, L.; Chen, B.; Tao, S.; Chiou, C.T.

2003-01-01

Sorption of organic contaminants (phenol, p-nitrophenol, and naphthalene) to natural solids (soils and bentonite) with and without myristylpyridinium bromide (MPB) cationic surfactant was studied to provide novel insight to interactions of contaminants with the mineral-adsorbed surfactant. Contaminant sorption coefficients with mineral-adsorbed surfactants, Kss, show a strong dependence on surfactant loading in the solid. At low surfactant levels, the Kss values increased with increasing sorbed surfactant mass, reached a maximum, and then decreased with increasing surfactant loading. The Kss values for contaminants were always higher than respective partition coefficients with surfactant micelles (Kmc) and natural organic matter (Koc). At examined MPB concentrations in water the three organic contaminants showed little solubility enhancement by MPB. At low sorbed-surfactant levels, the resulting mineral-adsorbed surfactant via the cation-exchange process appears to form a thin organic film, which effectively "adsorbs" the contaminants, resulting in very high Kss values. At high surfactant levels, the sorbed surfactant on minerals appears to form a bulklike medium that behaves essentially as a partition phase (rather than an adsorptive surface), with the resulting Kss being significantly decreased and less dependent on the MPB loading. The results provide a reference to the use of surfactants for remediation of contaminated soils/sediments or groundwater in engineered surfactant-enhanced washing.

Sugars levels of four sugarcane genotypes in different stem portions during the maturation phase.

PubMed

Pereira, Laís F M; Ferreira, Vilma M; Oliveira, Nelson G DE; Sarmento, Pedro L V S; Endres, Laurício; Teodoro, Iêdo

2017-01-01

Maturation is a characteristic of sugarcane plant (Saccharum spp.) and even when grown under the same soil and climate conditions the varieties differ on the maturation curve. Thus, studies that allow establishing maturation curves of different sugarcane genotypes in the local soil and climate may indicate the proper harvesting period to ensure better quality of the raw material. This study aimed to analyze the levels of soluble sugars during the maturation phase and assess the technological and productivity indexes of four irrigated sugarcane genotypes in the region of Rio Largo, Alagoas. The experiment was conducted in randomized blocks in a 4 x 2 x 5 factorial: four genotypes (RB92579, RB98710, RB99395 and RB961003), two stem portions (internodes 1-4 and internodes 5-8) and five seasons (82, 49, 25, 13 and 3 days before harvesting), each treatment with three replications. Internodes 1-4 showed the highest levels of reducing sugars, while the largest accumulation of sucrose and total soluble solids occurred in internodes 5-8. RB99395 genotype showed more stability in the sugar levels during sugarcane maturation, which can indicate early maturation and high agricultural yield.

Quantitative analysis of three chiral pesticide enantiomers by high-performance column liquid chromatography.

PubMed

Wang, Peng; Liu, Donghui; Gu, Xu; Jiang, Shuren; Zhou, Zhiqiang

2008-01-01

Methods for the enantiomeric quantitative determination of 3 chiral pesticides, paclobutrazol, myclobutanil, and uniconazole, and their residues in soil and water are reported. An effective chiral high-performance liquid chromatographic (HPLC)-UV method using an amylose-tris(3,5-dimethylphenylcarbamate; AD) column was developed for resolving the enantiomers and quantitative determination. The enantiomers were identified by a circular dichroism detector. Validation involved complete resolution of each of the 2 enantiomers, plus determination of linearity, precision, and limit of detection (LOD). The pesticide enantiomers were isolated by solvent extraction from soil and C18 solid-phase extraction from water. The 2 enantiomers of the 3 pesticides could be completely separated on the AD column using n-hexane isopropanol mobile phase. The linearity and precision results indicated that the method was reliable for the quantitative analysis of the enantiomers. LODs were 0.025, 0.05, and 0.05 mg/kg for each enantiomer of paclobutrazol, myclobutanil, and uniconazole, respectively. Recovery and precision data showed that the pretreatment procedures were satisfactory for enantiomer extraction and cleanup. This method can be used for optical purity determination of technical material and analysis of environmental residues.

The identification of carbamazepine biodegrading phylotypes and phylotypes sensitive to carbamazepine exposure in two soil microbial communities.

PubMed

Thelusmond, Jean-Rene; Strathmann, Timothy J; Cupples, Alison M

2016-11-15

Carbamazepine (CBZ), an antiepileptic drug, has been introduced into agricultural soils via irrigation with treated wastewater and biosolids application. Such contamination is problematic because CBZ is persistent and the risks to ecosystems or human health are unknown. The current study examined CBZ biodegradation in two agricultural soils (soil 1 and 2) and the effects on the soil microbial communities during CBZ exposure. The experimental design involved three CBZ concentrations (50, 500, 5000ng/g), under aerobic as well as anaerobic conditions. CBZ concentrations were determined using solid phase extraction and LC MS/MS. The effect of CBZ on the soil microbial community was investigated using high throughput sequencing and a computational approach to predict functional composition of the metagenomes (phylogenetic investigation of communities by reconstruction of unobserved states, PICRUSt). The most significant CBZ biodegradation occurred in soil 1 under aerobic conditions. In contrast, CBZ biodegradation was limited under anaerobic conditions in soil 1 and under both conditions in soil 2. For soil 1, several phylotypes were enriched following CBZ degradation compared to the controls, including unclassified Sphingomonadaceae, Xanthomonadaceae and Rhodobacteraceae, as well as Sphingomonas, Aquicella and Microvirga. These phylotypes are considered putative CBZ degraders as they appear to be benefiting from CBZ biodegradation. PICRUSt revealed that soil 1 contained a greater abundance of xenobiotic degrading genes compared to soil 2, and thus, this analysis method offers a potential valuable approach for predicting CBZ attenuation in soils. PICRUSt analysis also implicated Sphingomonadaceae and Xanthomonadaceae in drug metabolism. Interestingly, numerous phylotypes decreased in abundance following CBZ exposure and these varied with soil type, concentration, duration of exposure, and the availability of oxygen. For three phylotypes (Flavobacterium, 3 genus incertae sedis and unclassified Bacteroidetes), the relative abundance was reduced in both soils, indicating a notable sensitivity to CBZ for these microorganisms. Copyright © 2016 Elsevier B.V. All rights reserved.

Retention of silver nano-particles and silver ions in calcareous soils: Influence of soil properties.

PubMed

Rahmatpour, Samaneh; Shirvani, Mehran; Mosaddeghi, Mohammad R; Bazarganipour, Mehdi

2017-05-15

The rapid production and application of silver nanoparticles (AgNPs) have led to significant release of AgNPs into the terrestrial environments. Once released into the soil, AgNPs could enter into different interactions with soil particles which play key roles in controlling the fate and transport of these nanoparticles. In spite of that, experimental studies on the retention of AgNPs in soils are very scarce. Hence, the key objective of this research was to find out the retention behavior of AgNPs and Ag(I) ions in a range of calcareous soils. A second objective was to determine the extent to which the physico-chemical properties of the soils influence the Ag retention parameters. To this end, isothermal batch experiments were used to determine the retention of Poly(vinylpyrrolidinone)-capped AgNPs (PVP-AgNPs) and Ag(I) ions by nine calcareous soils with a diversity of physico-chemical properties. The results revealed that the retention data for both PVP-AgNPs and Ag(I) ions were well described by the classical Freundlich and Langmuir isothermal equations. The retention of PVP-AgNPs and Ag(I) ions was positively correlated to clay and organic carbon (OC) contents as well as electrical conductivity (EC), pH, and cation exchange capacity (CEC) of the soils. Due to multicolinearity among the soil properties, principal component analysis (PCA) was used to group the soil properties which affect the retention of PVP-AgNPs and Ag(I) ions. Accordingly, we identified two groups of soil properties controlling retention of PVP-AgNPs and Ag(I) ions in the calcareous soils. The first group comprised soil solid phase parameters like clay, OC, and CEC, which generally control hetero-aggregation and adsorption reactions and the second group included soil solution variables such as EC and pH as well as Cl - and Ca 2+ concentrations, which are supposed to mainly affect homo-aggregation and precipitation reactions. Copyright © 2017. Published by Elsevier Ltd.

Influences of quaternary climatic changes on processes of soil development on desert loess deposits of the Cima volcanic field, California

USGS Publications Warehouse

McFadden, L.D.; Wells, S.G.; Dohrenwend, J.C.

1986-01-01

Soils formed in loess are evidence of both relict and buried landscapes developed on Pliocene-to-latest Pleistocene basalt flows of the Cima volcanic field in the eastern Mojave Desert, California. The characteristics of these soils change systematically and as functions of the age and surface morphology of the lava flow. Four distinct phases of soil development are recognized: phase 1 - weakly developed soils on flows less than 0.18 M.y. old; phase 2 - strongly developed soils with thick argillic horizons on 0.18 - 0.7 M.y. old flows; phase 3 - strongly developed soils with truncated argillic horizons massively impregnated by carbonate on 0.7 to 1.1 M.y. old flows; and phase 4 - degraded soils with petrocalcic rubble on Pliocene flows. A critical aspect of the development of stage 1 soils is the evolution of a vesicular A horizon which profoundly affects the infiltration characteristics of the loess parent materials. Laboratory studies show that secondary gypsum and possibly other salt accumulation probably occurred during the period of phase 1 soil development. Slight reddening of the interiors of peds from vesicular-A horizons of phase 1 soils and presence of weakly developed B horizons indicates a slight degree of in situ chemical alteration. However, clay and Fe oxide contents of these soils show that these constituents, as well as carbonates and soluble salts, are incorporated as eolian dust. In contrast to phase 1 soils, chemical and mineralogical analysis of argillic horizons of phase 2 soils indicate proportionally greater degrees of in-situ chemical alteration. These data, the abundant clay films, and the strong reddening in the thick argillic horizons suggest that phase 2 and phase 3 soils formed during long periods of time and periodically were subjected to leaching regimes more intense than those that now exist. Flow-age data and soil-stratigraphic evidence also indicate that several major loess-deposition events occurred during the past ??? 1.0 M.y. Loess events are attributed to past changes in climate, such as the Pleistocene-to-Holocene climatic change, that periodically caused regional desiccation of pluvial lakes, reduction of vegetational density, and exposure of loose, unconsolidated fine materials. During times of warmer interglacial climates, precipitation infiltrates to shallower depths than during glacial periods. Extensive, saline playas which developed in the Mojave Desert during the Holocene are a likely source of much of the carbonates and soluble salts that are accumulating at shallow depths both in phase 1 soils and in the formerly noncalcareous, nongypsiferous argillic horizons of phase 2 and 3 soils. ?? 1986.

Fate and transport of lignin in the soil-water continuum

NASA Astrophysics Data System (ADS)

Williams, J. S.; Dungait, J.; Bol, R.; Abbott, G. D.

2011-12-01

Soils have been identified as having the potential to store greater amounts of carbon (C) in soil organic matter (SOM) through appropriate land uses and management practices to increase the input of recalcitrant components of organic matter, such as lignin. Lignin is allocated to the 'slow' soil C pools with residence times between 15 - 100 yrs. Lignin is 30% of the C fixed by plants and is an important C input to soils. However, Recent research has shown that the configuration of lignin monomers within the lignin macromolecule is not random [1], that lignin degradation is monomer specific [2], and that lignin is preferentially degraded relative to the bulk SOM [3], thereby questioning the role of lignin in C sequestration. Although guaiacyl (G) and syringyl (S) lignin monomers have been identified in fresh, estuarine, and marine waters [4], the initial forms to which lignin is degraded into water-transportable products and lost from the soil C reservoir are not known. The aims of this project are to (i) identify and quantify the lignin-derived products entering the soluble phase in soils, and (ii) determine the rate of lignin degradation into water-soluble components, and their rate of transport through soil. In experiment 1 we tested the best approach to extract and analyse dissolved lignin from outflows from grassland and woodland sites. C18 solid phase extraction (SPE) or freeze-drying (FD) was used to isolate water-borne lignin monomers. Gas chromatography-mass spectrometry (GC-MS) of trimethylsilyl (TMS) derivatives or tetramethylammonium hydroxide (TMAH) thermochemolysis was used to analyse the samples. In a subsequent experiment, we allowed leaves from different vegetation types (Lolium perenne, Ranunculus repens, Fraxinus excelsior, Quercus robur), corresponding to the vegetation at our initial sites in Experiment 1, to degrade in soil lysimeters for 1.5 years to determine the rates of decomposition of different plant material and dominant form of lignin moving into the aqueous phase in each case. Our results showed that C18 silica-based SPE recovered a greater proportion of detectable dissolved lignin than FD both in terms of number of compounds identified as well as total mass of lignin. More lignin-derived compounds were identified using TMAH/GC-MS than GC-MS of TMS derivatives. The lysimeter experiment showed that Ranunculus repens and Lolium perenne decomposition was most rapid and generated the highest leachate TOC values. TMAH/GC/MS analysis identified G, S, and p-hydroxyphenyl (P) units in the vegetation leachates with side-chains ranging from one to three carbons, with varying degrees of oxidation. This research provides new insight into the complexity of lignin breakdown and movement through soils.

Groundwater dynamics in wetland soils control the production and transfer mechanisms of dissolved reactive phosphorus in an agricultural landscape

NASA Astrophysics Data System (ADS)

Dupas, Rémi; Gu, Sen; Gruau, Gérard; Gascuel-Odoux, Chantal

2015-04-01

Because of its high sorption affinity on soils solid phase, mitigation options to reduce diffuse P transfer usually focus on trapping particulate P forms delivered via surface flowpaths. Therefore, vegetated buffer zones placed between croplands and watercourses have been promoted worldwide, sometimes in wetland areas. To investigate the risk of such P trapping riparian wetlands (RWs) releasing dissolved P to rivers, we monitored molybdate reactive P (MRP) in the free soil solution of two RWs in an intensively farmed catchment. Two main mechanisms causing MRP release were identified in light of the geochemical and hydrological conditions in the RWs, controlled by groundwater dynamics. First, soil rewetting after the dry summer was associated with the presence of a pool of mobile P, limited in size. Its mobilization started under conditions of water saturation caused by groundwater uprise in RW organo-mineral soil horizons. Second, the establishment of anoxic conditions in the end of the winter caused reductive solubilization of Fe oxide-hydroxide, along with release of P. Comparison between sites revealed that the first MRP release occurred only in a RW with P enriched soils, whereas the second was recorded even in a RW with a low soil P status. Seasonal variations in MRP concentrations in the stream were synchronized with those in RW soils. Hence, enriched and/or periodically anoxic RWs can act as a key component of the P transfer continuum in agricultural landscapes by converting particulate P from croplands into MRP released to rivers.

Sandy Soil Microaggregates: Rethinking Our Understanding of Hydraulic Function

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paradiś, Ashley; Brueck, Christopher; Meisenheimer, Douglas

2017-01-01

This study investigated the peculiar structure of microaggregates in coarse sandy soils that exhibit only external porosity and investigated their control on soil hydrology. The microstructure underpins a hydrologic existence that differs from finer textured soils where aggregates have internal porosity. Understanding the impact of these microaggregates on soil hydrology will permit improved agricultural irrigation management and estimates associated with ecosystem capacity and resiliency. Microstructure was investigated using a digital microscope, and aspects of the structure were quantified by sedimentation and computed microtomography. Sandy soil microaggregates were observed to be comprised of a solid sand-grain core that is coated withmore » fines, presumably cemented by organic media. This microstructure leads to three distinct water pools during drainage: capillary water, followed by thick films (1–20 μm) enveloping the outer surfaces of the crusted microaggregates, followed by adsorbed thin films (<1 μm). The characteristics of the thick films were investigated using an analytical model. These films may provide as much as 10 to 40% saturation in the range of plant-available water. Using lubrication theory, it was predicted that thick film drainage follows a power law function with an exponent of 2. Thick films may also have a role in the geochemical evolution of soils and in ecosystem function because they provide contiguous water and gas phases at relatively high moisture contents. And, because the rough outer crust of these microaggregates can provide good niches for microbial activity, biofilm physics will dominate thick film processes, and consequently hydrologic, biologic, and geochemical functions for coarse sandy soils.« less

Mechanistic insights from DGT and soil solution measurements on the uptake of Ni and Cd by radish.

PubMed

Luo, Jun; Cheng, Hao; Ren, Jinghua; Davison, William; Zhang, Hao

2014-07-01

This work tests the previously proposed hypothesis that plant uptake of metals is determined dominantly by diffusional controlled or plant limiting uptake mechanisms at, respectively, low and high metal concentrations. Radish (Raphanus sativus) was grown in 13 soils spiked with Ni (10 and 100 mg kg(-1)) and Cd (0.5 and 4 mg kg(-1)) for 4 weeks to investigate the mechanisms affecting plant uptake. Soil solution concentrations, Css, of Ni and Cd were measured, along with the DGT interfacial concentration, CDGT, and the derived effective concentration in soil solution, CE. Free ion activities, aNi(2+) and aCd(2+), were obtained using WHAM 6. Although there was a poor relationship between Ni in radish roots and either Css or aNi(2+) in unamended soils, the distribution of data could be rationalized in terms of the extent of release of Ni from the soil solid phase, as identified by DGT and soil solution measurements. By contrast Ni in radish was linearly related to CE, demonstrating diffusion limited uptake. For soils amended with high concentrations of Ni, linear relationships were obtained for Ni in radish plotted against, Css, aNi(2+), and CE, consistent with the plant controlling uptake. For Ni the hypothesis concerning dominant diffusional and plant limiting uptake mechanisms was demonstrated. Poor relationships between Cd in radish and Css, aCd(2+), and CE, irrespective of amendment by Cd, showed the importance of factors other than diffusional supply, such as rhizosphere and inhibitory processes, and that fulfilment of this hypothesis is plant and metal specific.

Three modified activated carbons by different ligands for the solid phase extraction of copper and lead.

PubMed

Ghaedi, M; Ahmadi, F; Tavakoli, Z; Montazerozohori, M; Khanmohammadi, A; Soylak, M

2008-04-15

In the presented work, 5,5-diphenylimidazolidine-2,4-dione (phenytoin) (DFTD), 5,5-diphenylimidazolidine-2-thione-,4-one (thiophenytoin) (DFID) and 2-(4'-methoxy-benzylidenimine) thiophenole (MBIP) modified activated carbons have been used for the solid phase extraction of copper and lead ions prior to their flame atomic absorption spectrometric determinations. The influences of the various analytical parameters including pH, amounts of reagent, sample volume and eluent type, etc. on the recovery efficiencies of copper and lead ions were investigated. The influences of alkaline, earth alkaline and some transition metals on the adsorption of the analytes were also examined. The detection limits by three sigma for analyte ions were 0.65 and 0.42 microg L(-1) using activated carbon modified with DFID; 0.52 and 0.37 microg L(-1) using activated carbon modified with DFTD and 0.46 and 0.31 microg L(-1) using activated carbon modified with MBIP for Pb(II) and Cu(II), respectively. The procedure was applied to the determination of analytes in natural waters, soil, and blood samples with satisfactory results (recoveries greater than 95%, R.S.D.'s lower than 4%).

Separation, preconcentration and inductively coupled plasma-mass spectrometric (ICP-MS) determination of thorium(IV), titanium(IV), iron(III), lead(II) and chromium(III) on 2-nitroso-1-naphthol impregnated MCI GEL CHP20P resin.

PubMed

Aydin, Funda Armagan; Soylak, Mustafa

2010-01-15

A simple and effective method is presented for the separation and preconcentration of Th(IV), Ti(IV), Fe(III), Pb(II) and Cr(III) by solid phase extraction on 2-nitroso-1-naphthol impregnated MCI GEL CHP20P resin prior to their inductively coupled plasma-mass spectrometric determinations. The influence of analytical parameters including pH of the aqueous solution, flow rates of sample and eluent solutions and sample volume on the quantitative recoveries of analyte ions was investigated. Matrix effects caused by the presence of alkali, earth alkali and some metal ions in the analyzed solutions were investigated. The presented solid phase extraction method was applied to BCR-144R Sewage Sludge (domestic origin), BCR-141R Calcareous Loam Soil, NIST 1568a Rice Flour and NIST 1577b Bovine Liver certified reference materials (CRMs) for the determination of analyte ions and the results were in good agreement with the certified values. The separation procedure presented was also applied to the various natural water samples collected from Turkey with satisfactory results.

Phased Array Approach To Retrieve Gases, Liquids, Or Solids From Subsurface And Subaqueous Geologic Or Man-Made Formations

DOEpatents

Rynne, Timothy M.; Spadaro, John F.; Iovenitti, Joe L.; Dering, John P.; Hill, Donald G.

1998-10-27

A method of enhancing the remediation of contaminated soils and ground water, production of oil and gas, and production of any solid, gas, and/or liquid from subsurface geologic and man-made formations including the steps of estimating the geometric boundaries of the region containing the material to be recovered, drilling a recovery well(s) into subsurface in a strategic location to recover the material of interest, establishing multiple sources of acoustical power in an array about and spaced-apart from the surface or at various depths below the surface in a borehole(s) and/or well(s), directing a volume of acoustical excitation from the sources into the region containing the material to be recovered, the excitation in the form of either controllable sinusoidal, square, pulsed, or various combinations of these three waveforms, and controlling the phasing, frequency, power, duration, and direction of these waveforms from the sources to increase and control the intensity of acoustical excitation in the region of the material to be recovered to enhance. the recovery of said material from the recovery well(s). The invention will augment any technology affecting the removal of materials from the subsurface.

Sequestration of Sr(II) By Calcium Oxalate - a Batch Uptake Study And EXAFS Analysis of Model Compounds And Reaction Products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singer, D.M.; Johnson, S.B.; Catalano, J.G.

Calcium oxalate monohydrate (CaC{sub 2}O{sub 4}{center_dot}H{sub 2}O -- abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II){sub aq} following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4--10, with initial Sr solution concentrations, [Sr]{sub aq}, ranging from 1 x 10{sup -4} to 1 x 10{sup -3} M and ionic strengths ranging of 0.001--0.1more » M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sr{sub aq} for two days, the solution Ca concentration, [Ca]{sup aq}, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sr{sub aq} removed from solution was nearly equal to the total [Ca]{sup aq} after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model to account for anharmonic effects in the EXAFS data. For Sr-bearing phases with low to moderate first-shell (Sr-O pair correlation) anharmonicity, the cumulant expansion model is sufficient for EXAFS fitting; however, for higher degrees of anharmonicity, an analytical model is required. Based on batch uptake results and EXAFS analyses of reaction products, we conclude that Sr is dominantly sequestered by a solid phase at the CaOx surface, likely the result of a dissolution-reprecipitation mechanism, to form SrC{sub 2}O{sub 4} of mixed hydration state (i.e. SrO{sub x}{center_dot}nH{sub 2}O, where n = 0, 1, or 2). Surprisingly, no spectroscopic or XRD evidence was found for a (Sr,Ca)Ox solid solution or for a separate SrCO3 phase. In addition, we found no evidence for Sr(II) inner-sphere sorption complexes on CaOx surfaces based on lack of Sr-Ca second-neighbor pair correlations in the EXAFS spectra, although some type of Sr(II) surface complex (perhaps a type B Sr-oxalate ternary complex or an outer-sphere Sr(II) complex) or some as yet undetected Sr-bearing solid phases are needed to account for approximately 10% of Sr uptake by CaOx. The formation of a hydrated SrOx phase in environments under conditions similar to those of our experiments should retard Sr mobility and could be a significant factor in the biogeochemical cycling of Sr in soils and sediments or in plants and plant litter where CaOx is present.« less

40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

Code of Federal Regulations, 2010 CFR

2010-07-01

... solid phases of a material. 227.32 Section 227.32 Protection of Environment ENVIRONMENTAL PROTECTION... MATERIALS Definitions § 227.32 Liquid, suspended particulate, and solid phases of a material. (a) For the... obtained above prior to centrifugation and filtration. The solid phase includes all material settling to...

40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

Code of Federal Regulations, 2011 CFR

2011-07-01

... solid phases of a material. 227.32 Section 227.32 Protection of Environment ENVIRONMENTAL PROTECTION... MATERIALS Definitions § 227.32 Liquid, suspended particulate, and solid phases of a material. (a) For the... obtained above prior to centrifugation and filtration. The solid phase includes all material settling to...

Variable Charge Soils: Mineralogy and Chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Nik; Van Ranst, Eric; Noble, Andrew

2003-11-01

Soils rich in particles with amphoteric surface properties in the Oxisols, Ultisols, Alfisols, Spodosols and Andisols orders (1) are considered variable charge soils (2). The term “variable charge” is used to describe organic and inorganic soil constituents with reactive surface groups whose charge varies with pH, ionic concentration and composition of the soil solution. Such groups are the surface carboxyl, phenolic and amino functional groups of organic materials in soils, and surface hydroxyl groups of Fe and Al oxides, allophane and imogolite. The hydroxyl surface groups are also present on edges of some phyllosilicate minerals such as kaolinite, mica, andmore » hydroxyl-interlayered vermiculite. The variable charge is developed on the surface groups as a result of adsorption or desorption of ions that are constituents of the solid phase, i.e., H+, and the adsorption or desorption of solid-unlike ions that are not constituents of the solid. Highly weathered soils usually undergo isoeletric weathering and reach a “zero net charge” stage during their development. They have a slightly acidic to acidic soil solution pH, which is close to either point of zero net charge (PZNC) (3) or point of zero salt effect (PZSE) (3). They are characterized by high abundances of minerals with a point of zero net proton charge (PZNPC) (3) at neutral and slightly basic pHs; the most important being Fe and Al oxides and allophane. Under acidic conditions, the surfaces of these minerals are net positively charged. In contrast, the surfaces of permanent charge phyllosilicates are negatively charged regardless of ambient conditions. Variable charge soils therefore, are heterogeneous charge systems. The coexistence and interactions of oppositely charged surfaces or particles confers a different pattern of physical and chemical behavior on the soil, relatively to a homogeneously charged system of temperate regions. In some variable charge soils (Oxisols and some Ultisols developed on ferromagnesian-rich parent materials) the surfaces of phyllosilicates are coated to a lesser or greater extent by amorphous or crystalline, oppositely charged nanoparticles of Fe and Al oxides. These coatings exhibit a high reactive surface area and help cementing larger particles with one another. As a result of these electrostatic interactions, stable microaggregates that are difficult to disperse are formed in variable charge soils. Most of highly weathered soils have reached the “advanced stage” of Jackson-Sherman weathering sequence that is characterized by the removal of Na, K, Ca, Mg, and Fe(II), the presence of Fe and Al polymers, and very dilute soil solutions with an ionic strength (IS) of less than 1 mmol L-1. The inter-penetration or overlapping of the diffuse double layers on oppositely charged surfaces may occur in these dilute systems. These diffuse layer interactions may affect the magnitude of the effective charge, i.e., the counter-ion charge (4). In addition, salt adsorption, which is defined as the simultaneous adsorption in equivalent amounts of the cation and anion of an electrolyte with no net release of other ions into the soil solution, appears to be a common phenomenon in these soils. They act as cation- and anion-exchangers and as salt-sorbers. The magnitude of salt adsorption depends strongly on initial IS in the soil solution and the presence in appreciable amounts of oppositely charged surfaces. Among the authors that have made illustrious contributions towards a better understanding of these fascinating soil systems are S. Matson, R.K. Schofield, van Olphen, M.E. Sumner, G.W. Thomas, G.P. Gillman, G. Uehara, B.K.G. Theng, K. Wada, N.J. Barrow, J.W. Bowden, R.J. Hunter and G. Sposito. This entry is mainly based on publications by these authors.« less

Occurrence of select perfluoroalkyl substances at U.S. Air Force aqueous film-forming foam release sites other than fire-training areas: Field-validation of critical fate and transport properties.

PubMed

Anderson, R Hunter; Long, G Cornell; Porter, Ronald C; Anderson, Janet K

2016-05-01

The use of aqueous film-forming foam (AFFF) to extinguish hydrocarbon-based fires is recognized as a significant source of environmental poly- and perfluoroalkyl substances (PFASs). Although the occurrence of select PFASs in soil and groundwater at former fire-training areas (FTAs) at military installations operable since 1970 has been consistently confirmed, studies reporting the occurrence of PFASs at other AFFF-impacted sites (e.g. emergency response locations, AFFF lagoons, hangar-related AFFF storage tanks and pipelines, and fire station testing and maintenance areas) are largely missing from the literature. Further, studies have mostly focused on a single site (i.e., FTAs at military installations) and, thus, lack a comparison of sites with diverse AFFF release history. Therefore, the purpose of this investigation was to evaluate select PFAS occurrence at non-FTA sites on active U.S. Air Force installations with historic AFFF use of varying magnitude. Concentrations of fifteen perfluoroalkyl acids (PFAAs) and perfluorooctane sulfonamide (PFOSA), an important PFOS precursor, were measured from several hundred samples among multiple media (i.e., surface soil, subsurface soil, sediment, surface water, and groundwater) collected from forty AFFF-impacted sites across ten installations between March and September 2014, representing one of the most comprehensive datasets on environmental PFAS occurrence to date. Differences in detection frequencies and observed concentrations due to AFFF release volume are presented along with rigorous data analyses that quantitatively demonstrate phase-dependent (i.e., solid-phase vs aqueous-phase) differences in the chemical signature as a function of carbon chain-length and in situ PFOS (and to a slightly lesser extent PFHxS) formation, presumably due to precursor biotransformation. Published by Elsevier Ltd.

Modeling the effect of soil structure on water flow and isoproturon dynamics in an agricultural field receiving repeated urban waste compost application.

PubMed

Filipović, Vilim; Coquet, Yves; Pot, Valérie; Houot, Sabine; Benoit, Pierre

2014-11-15

Transport processes in soils are strongly affected by heterogeneity of soil hydraulic properties. Tillage practices and compost amendments can modify soil structure and create heterogeneity at the local scale within agricultural fields. The long-term field experiment QualiAgro (INRA-Veolia partnership 1998-2013) explores the impact of heterogeneity in soil structure created by tillage practices and compost application on transport processes. A modeling study was performed to evaluate how the presence of heterogeneity due to soil tillage and compost application affects water flow and pesticide dynamics in soil during a long-term period. The study was done on a plot receiving a co-compost of green wastes and sewage sludge (SGW) applied once every 2 years since 1998. The plot was cultivated with a biannual rotation of winter wheat-maize (except 1 year of barley) and a four-furrow moldboard plow was used for tillage. In each plot, wick lysimeter outflow and TDR probe data were collected at different depths from 2004, while tensiometer measurements were also conducted during 2007/2008. Isoproturon concentration was measured in lysimeter outflow since 2004. Detailed profile description was used to locate different soil structures in the profile, which was then implemented in the HYDRUS-2D model. Four zones were identified in the plowed layer: compacted clods with no visible macropores (Δ), non-compacted soil with visible macroporosity (Γ), interfurrows created by moldboard plowing containing crop residues and applied compost (IF), and the plow pan (PP) created by plowing repeatedly to the same depth. Isoproturon retention and degradation parameters were estimated from laboratory batch sorption and incubation experiments, respectively, for each structure independently. Water retention parameters were estimated from pressure plate laboratory measurements and hydraulic conductivity parameters were obtained from field tension infiltrometer experiments. Soil hydraulic properties were optimized on one calibration year (2007/08) using pressure head, water content and lysimeter outflow data, and then tested on the whole 2004/2010 period. Lysimeter outflow and water content dynamics in the soil profile were correctly described for the whole period (model efficiency coefficient: 0.99) after some correction of LAI estimates for wheat (2005/06) and barley (2006/07). Using laboratory-measured degradation rates and assuming degradation only in the liquid phase caused large overestimation of simulated isoproturon losses in lysimeter outflow. A proper order of magnitude of isoproturon losses was obtained after considering that degradation occurred in solid (sorbed) phase at a rate 75% of that in liquid phase. Isoproturon concentrations were found to be highly sensitive to degradation rates. Neither the laboratory-measured isoproturon fate parameters nor the independently-derived soil hydraulic parameters could describe the actual multiannual field dynamics of water and isoproturon without calibration. However, once calibrated on a limited period of time (9 months), HYDRUS-2D was able to simulate the whole 6-year time series with good accuracy. Copyright © 2014 Elsevier B.V. All rights reserved.

SUPERFUND TREATABILITY CLEARINGHOUSE: BDAT FOR SOLIDIFICATION/STABILIZATION TECHNOLOGY FOR SUPERFUND SOILS (DRAFT FINAL REPORT)

EPA Science Inventory

This report evaluates the performance of solidification as a method for treating solids from Superfund sites. Tests were conducted on four different artificially contaminated soils which are representative of soils found at the sites. Contaminated soils were solidified us...

Speciation of selenium in environmental samples by solid-phase spectrophotometry using 2,3-dichloro-6-(2,7-dihydroxy-naphthylazo)quinoxaline.

PubMed

Amin, Alaa S

2014-01-01

Solid-phase spectrophotometry was applied to determination of trace amounts of selenium (Se) in water, soil, plant materials, human hair, and a cosmetic preparation (lipstick). Se(IV) was sorbed in a dextran type lipophilic gel as a complex with 2,3-dichloro-6-(2,7-dihydroxy-naphthylazo)quinoxaline (DCDHNAQ), whereas Se(VI) was determined after boiling in HCI for 10 min to convert Se(VI) to Se(IV). Resin phase absorbances at 588 and 800 nm were measured directly, which allowed the determination of Se in the range of 0.2-3.3 microg/L with an RSD of 1.22%. The influences of analytical parameters including pH of the aqueous solution, amounts of DCDHNAQ, and sample volume were investigated. The molar absorptivities were found to be 1.09 x 10(6), 4.60 x 10(6), and 1.23 x 10(7) L/mol cm for 100, 500, and 1000 mL, respectively. The LOD and LOQ of the 500 mL sample method were 110 and 360 ng/L, respectively, when using 50 mg dextran type lipophilic gel. For a 1000 mL sample, the LOD and LOQ were 60 and 200 ng/L, respectively, using 50 mg of the exchanger. Increasing the sample volume enhanced the sensitivity. No considerable interferences were observed from other investigated anions and cations on the Se determination.

Pesticide interactions with soils affected by olive oil mill wastewater

NASA Astrophysics Data System (ADS)

Keren, Yonatan; Bukhanovsky, Nadezhda; Borisover, Mikhail

2013-04-01

Soil pesticide sorption is well known to affect the fate of pesticides, their bioavailability and the potential to contaminate air and water. Soil - pesticide interactions may be strongly influenced by soil organic matter (SOM) and organic matter (OM)-rich soil amendments. One special OM source in soils is related to olive oil production residues that may include both solid and liquid wastes. In the Mediterranean area, the olive oil production is considered as an important field in the agricultural sector. Due to the significant rise in olive oil production, the amount of wastes is growing respectively. Olive oil mill waste water (OMWW) is the liquid byproduct in the so-called "three phase" technological process. Features of OMWW include the high content of fatty aliphatic components and polyphenols and their often-considered toxicity. One way of OMWW disposal is the land spreading, e.g., in olive orchards. The land application of OMWW (either controlled or not) is supposed to affect the multiple soil properties, including hydrophobicity and the potential of soils to interact with pesticides. Therefore, there is both basic and applied interest in elucidating the interactions between organic compounds and soils affected by OMWW. However, little is known about the impact of OMWW - soil interactions on sorption of organic compounds, and specifically, on sorption of agrochemicals. This paper reports an experimental study of sorption interactions of a series of organic compounds including widely used herbicides such as diuron and simazine, in a range of soils that were affected by OMWW (i) historically or (ii) in the controlled land disposal experiments. It is demonstrated that there is a distinct increase in apparent sorption of organic chemicals in soils affected by OMWW. In selected systems, this increase may be explained by increase in SOM content. However, the SOM quality places a role: the rise in organic compound - soil interactions may both exceed the SOM content increase and be less than that. Sorption interactions of herbicides with soils demonstrate a strong hysteresis (which is not expected to be related to a biodegradation). The data suggests that the OMWW - soil interaction seems to change the shape of the apparent sorption isotherms of organic sorbates, and, possibly, their sorption mechanisms: from a Langmuir-like sorption isotherm (describing the adsorptive interactions with a saturation of sorption sites) in the native soils to the sigmoidal or linear isotherms (expected for a partitioning into the bulk OM phases and their swelling) in the OMWW-amended soils. These results may have a significant impact on multiple agricultural and hydrological aspects, e.g., such as the application rate of herbicides in the field, and their possible release and the long term effect on groundwater. The authors acknowledge the support from the OLIVEOIL project (SCHA849/13) funded by DFG.

Germanium/silicon ratios as a tracer of silica sources in Hawaiian streams

NASA Astrophysics Data System (ADS)

Kurtz, A.; Derry, L.; Chadwick, O.

2003-04-01

Ge/Si ratios show great promise as a tracer of terrestrial silica cycling, weathering, and hydrologic flowpaths in catchment studies. Germanium is a trace element whose behavior mimics silicon in most environments. Silicate weathering fractionates Ge/Si though preferential incorporation of Ge in secondary clays. Dissolved Ge/Si ratios of most streams 1) are lower than those in the rocks they drain, 2) vary with discharge, and 3) fall on a two-component mixing curve when plotted against [Si]. These observations have led to the suggestion that streamwater Ge/Si ratios trace watershed-integrated weathering intensity, via mixing between a high [Si], low Ge/Si component derived from incongruent weathering of primary silicates, and a low [Si], high Ge/Si component derived from dissolution of secondary minerals. We tested this model by measuring depth profiles of soil and soil-water [Si] and Ge/Si ratios from six sites along a soil chronosequence in Hawaii. Soils range from incipiently weathered at the young (300 year-old substrate) end of the chronosequence to intensely weathered in soils older than 20,000 years. All sites have essentially identical parent material, climate (250 cm rain/year), and vegetation (Ohia and tree-ferns). Solid-phase Ge/Si in these soils increase with silica depletion from basalt-like values of 2.5 µmol/mol in young soils to values > 20 µmol/mol as Ge is preferentially retained by secondary phases in older soils. Soil-water compositions depend primarily on depth. Deep soil-waters (>20 cm) have low [Si] and high Ge/Si (1.5 to 5 µmol/mol), consistent with dissolution of Ge-enriched secondary minerals. Surface horizon soil-waters (<15cm) from all profiles have high [Si], in some cases approaching opal saturation, and low Ge/Si (0.3 to 1 µmol/mol). This component is consistent with dissolution of low Ge/Si terrestrial plant phytolith opal. We find no evidence that incongruent weathering contributes a high [Si], low Ge/Si soil-water component, even in young soils that still contain volcanic glass. Instead, Hawaiian streamwater Ge/Si ratios appear to trace mixing between phytolith-derived Si sourced in surface soils, and secondary mineral-derived Si sourced in deep soils. A compilation of published Ge/Si data from USGS-gauged Hawaiian streams indicates that all are dominated by this low Ge/Si, apparently phytolith-derived source of Si. Only watersheds draining well-developed soils ever show high Ge/Si ratios, and only during periods of high discharge. Mass balance calculations suggest that ~80% of the silica flux carried by studied Hawaiian streams is delivered to streams via the soil phytolith silica pool.

Interactions of low molecular weight aromatic acids and amino acids with goethite, kaolinite and bentonite with or without organic matter coating

NASA Astrophysics Data System (ADS)

Gao, Jiajia; Jansen, Boris; Cerli, Chiara; Kalbitz, Karsten

2015-04-01

Interaction of organic matter molecules with the soil's solid phase is a key factor influencing the stabilization of carbon in soils and thus forms a crucial aspect of the global carbon cycle. While subject of much research attention so far, we still have much to learn about such interactions at the molecular level; in particular in the light of competition between different classes of organic molecules and in the presence of previously adsorbed soil organic matter. We studied the interaction of a group of low molecular weight (LMW) aromatic acids (salicylic, syringic, vanillic and ferulic acid) and amino acids (lysine, glutamic, leucine and phenylalanine) on goethite, kaolinite and bentonite with and without previously adsorbed dissolved organic matter (DOM). For this we used batch experiments at pH = 6.0 where some of the organic compounds were positively charged (i.e. lysine) or negatively charged (i.e. glutamic and salicylic acid) while the minerals also displayed positively (i.e. goethite) or negatively charged surfaces (i.e. bentonite). We found much higher sorption of salicylic acid and lysine than other compounds. On the bare minerals we found a great variety of sorption strength, with salicylic acid strongly adsorbed, while syringic, vanillic and ferulic acid showed little or no adsorption. For the amino acids, protonated lysine showed a stronger affinity to negatively charged kaolinite and bentonite than other amino acids. While deprotonated glutamic acid showed the strongest adsorption on goethite. Leucine and phenylalanine showed hardly any adsorption on any of the minerals. When present concurrently, amino acids decreased the sorption of salicylic acid on the three types of mineral, while the presence of LMW aromatic acids increased the sorption of lysine on kaolinite and bentonite and the sorption of glutamic acid on goethite. The presence of previously adsorbed DOM reduced the sorption of salicylic acid and lysine. The results confirm that interactions of different classes of organic molecules with solid soil phases cannot be understood in isolation, but must be interpreted in the context of the presence of other classes of molecules. It seems that the presence of methoxy groups decreases the adsorption of aromatic acids to minerals. We did not find evidence for protein conditioning of any mineral surface, i.e. increased adsorption of aromatic acids after adsorption of amino acids.

Use and environmental occurrence of pharmaceuticals in freestall dairy farms with manured forage fields

USGS Publications Warehouse

Watanabe, Naoko; Bergamaschi, Brian A.; Loftin, Keith A.; Meyer, Michael T.; Harter, Thomas

2010-01-01

Environmental releases of antibiotics from concentrated animal feeding operations (CAFOs) are of increasing regulatory concern. This study investigates the use and occurrence of antibiotics in dairy CAFOs and their potential transport into first-encountered groundwater. On two dairies we conducted four seasonal sampling campaigns, each across 13 animal production and waste management systems and associated environmental pathways: application to animals, excretion to surfaces, manure collection systems, soils, and shallow groundwater. Concentrations of antibiotics were determined using on line solid phase extraction (OLSPE) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) with electrospray ionization (ESI) for water samples, and accelerated solvent extraction (ASE) LC/MS/MS with ESI for solid samples. A variety of antibiotics were applied at both farms leading to antibiotics excretion of several hundred grams per farm per day. Sulfonamides, tetracyclines, and their epimers/isomers, and lincomycin were most frequently detected. Yet, despite decades of use, antibiotic occurrence appeared constrained to within farm boundaries. The most frequent antibiotic detections were associated with lagoons, hospital pens, and calf hutches. When detected below ground, tetracyclines were mainly found in soils, whereas sulfonamides were found in shallow groundwater reflecting key differences in their physicochemical properties. In manure lagoons, 10 compounds were detected including tetracyclines and trimethoprim. Of these 10, sulfadimethoxine, sulfamethazine, and lincomycin were found in shallow groundwater directly downgradient from the lagoons. Antibiotics were sporadically detected in field surface samples on fields with manure applications, but not in underlying sandy soils. Sulfadimethoxine and sulfamethazine were detected in shallow groundwater near field flood irrigation gates, but at highly attenuated levels.

Use and environmental occurrence of antibiotics in freestall dairy farms with manured forage fields.

PubMed

Watanabe, Naoko; Bergamaschi, Brian A; Loftin, Keith A; Meyer, Michael T; Harter, Thomas

2010-09-01

Environmental releases of antibiotics from concentrated animal feeding operations (CAFOs) are of increasing regulatory concern. This study investigates the use and occurrence of antibiotics in dairy CAFOs and their potential transport into first-encountered groundwater. On two dairies we conducted four seasonal sampling campaigns, each across 13 animal production and waste management systems and associated environmental pathways: application to animals, excretion to surfaces, manure collection systems, soils, and shallow groundwater. Concentrations of antibiotics were determined using on line solid phase extraction (OLSPE) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) with electrospray ionization (ESI) for water samples, and accelerated solvent extraction (ASE) LC/MS/MS with ESI for solid samples. A variety of antibiotics were applied at both farms leading to antibiotics excretion of several hundred grams per farm per day. Sulfonamides, tetracyclines, and their epimers/isomers, and lincomycin were most frequently detected. Yet, despite decades of use, antibiotic occurrence appeared constrained to within farm boundaries. The most frequent antibiotic detections were associated with lagoons, hospital pens, and calf hutches. When detected below ground, tetracyclines were mainly found in soils, whereas sulfonamides were found in shallow groundwater reflecting key differences in their physicochemical properties. In manure lagoons, 10 compounds were detected including tetracyclines and trimethoprim. Of these 10, sulfadimethoxine, sulfamethazine, and lincomycin were found in shallow groundwater directly downgradient from the lagoons. Antibiotics were sporadically detected in field surface samples on fields with manure applications, but not in underlying sandy soils. Sulfadimethoxine and sulfamethazine were detected in shallow groundwater near field flood irrigation gates, but at highly attenuated levels.

Use and Environmental Occurrence of Antibiotics in Freestall Dairy Farms with Manured Forage Fields

PubMed Central

2010-01-01

Environmental releases of antibiotics from concentrated animal feeding operations (CAFOs) are of increasing regulatory concern. This study investigates the use and occurrence of antibiotics in dairy CAFOs and their potential transport into first-encountered groundwater. On two dairies we conducted four seasonal sampling campaigns, each across 13 animal production and waste management systems and associated environmental pathways: application to animals, excretion to surfaces, manure collection systems, soils, and shallow groundwater. Concentrations of antibiotics were determined using on line solid phase extraction (OLSPE) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) with electrospray ionization (ESI) for water samples, and accelerated solvent extraction (ASE) LC/MS/MS with ESI for solid samples. A variety of antibiotics were applied at both farms leading to antibiotics excretion of several hundred grams per farm per day. Sulfonamides, tetracyclines, and their epimers/isomers, and lincomycin were most frequently detected. Yet, despite decades of use, antibiotic occurrence appeared constrained to within farm boundaries. The most frequent antibiotic detections were associated with lagoons, hospital pens, and calf hutches. When detected below ground, tetracyclines were mainly found in soils, whereas sulfonamides were found in shallow groundwater reflecting key differences in their physicochemical properties. In manure lagoons, 10 compounds were detected including tetracyclines and trimethoprim. Of these 10, sulfadimethoxine, sulfamethazine, and lincomycin were found in shallow groundwater directly downgradient from the lagoons. Antibiotics were sporadically detected in field surface samples on fields with manure applications, but not in underlying sandy soils. Sulfadimethoxine and sulfamethazine were detected in shallow groundwater near field flood irrigation gates, but at highly attenuated levels. PMID:20698525

Ultrasensitive Speciation Analysis of Mercury in Rice by Headspace Solid Phase Microextraction Using Porous Carbons and Gas Chromatography-Dielectric Barrier Discharge Optical Emission Spectrometry.

PubMed

Lin, Yao; Yang, Yuan; Li, Yuxuan; Yang, Lu; Hou, Xiandeng; Feng, Xinbin; Zheng, Chengbin

2016-03-01

Rice consumption is a primary pathway for human methylmercury (MeHg) exposure in inland mercury mining areas of Asia. In addition, the use of iodomethane, a common fumigant that significantly accelerates the methylation of mercury in soil under sunlight, could increase the MeHg exposure from rice. Conventional hyphenated techniques used for mercury speciation analysis are usually too costly for most developing countries. Consequently, there is an increased interest in the development of sensitive and inexpensive methods for the speciation of mercury in rice. In this work, gas chromatography (GC) coupled to dielectric barrier discharge optical emission spectrometry (DBD-OES) was developed for the speciation analysis of mercury in rice. Prior to GC-DBD-OES analysis, mercury species were derivatized to their volatile species with NaBPh4 and preconcentrated by headspace solid phase microextraction using porous carbons. Limits of detection of 0.5 μg kg(-1) (0.16 ng), 0.75 μg kg(-1) (0.24 ng), and 1.0 μg kg(-1) (0.34 ng) were obtained for Hg(2+), CH3Hg(+), and CH3CH2Hg(+), respectively, with relative standard deviations (RSDs) better than 5.2% and 6.8% for one fiber or fiber-to-fiber mode, respectively. Recoveries of 90-105% were obtained for the rice samples, demonstrating the applicability of the proposed technique. Owing to the small size, low power, and low gas consumption of DBD-OES as well as efficient extraction of mercury species by porous carbons headspace solid phase micro-extraction, the proposed technique provides several advantages including compactness, cost-effectiveness, and potential to couple with miniature GC to accomplish the field speciation of mercury in rice compared to conventional hyphenated techniques.

Influence of soil-water ratio on the performance of slurry phase bioreactor treating herbicide contaminated soil.

PubMed

Venkata Mohan, S; Ramakrishna, M; Shailaja, S; Sarma, P N

2007-09-01

The influence of soil-water ratio was studied on the performance of the slurry phase bioreactor operated in sequencing batch mode (anoxic-aerobic-anoxic microenvironments) during the bioremediation of soil contaminated with pendimethalin. The performance of the reactors was evaluated at different soil-water ratios (1:5-1:25; at soil loading rate (60 kg of soil/cum-day to 12 kg of soil/cum-day)) keeping the loading rate of pendimethalin constant (133.2 g/kg of soil-day) in six reactors and variable (66.6 g/kg of soil-day to 166.6 g/kg of soil-day) in other four reactors. At 1:20 soil-water ratio, the slurry phase system showed enhanced degradation of substrate (629 microg pendimethalin/g soil). The removal efficiency of pendimethalin in the reactors was dependent on the mass-transfer rates of the substrate from the soil to the aqueous phase. Soil-water ratio and substrate loading rates showed significant influence on the substrate portioning, substrate degradation efficiency and substrate desorption rate.

Novel Culturing Techniques Select for Heterotrophs and Hydrocarbon Degraders in a Subantarctic Soil

PubMed Central

van Dorst, J. M.; Hince, G.; Snape, I.; Ferrari, B. C.

2016-01-01

The soil substrate membrane system (SSMS) is a novel micro-culturing technique targeted at terrestrial soil systems. We applied the SSMS to pristine and diesel fuel spiked polar soils, along with traditional solid media culturing and culture independent 454 tag pyrosequencing to elucidate the effects of diesel fuel on the soil community. The SSMS enriched for up to 76% of the total soil diversity within high diesel fuel concentration soils, in contrast to only 26% of the total diversity for the control soils. The majority of organisms originally recovered with the SSMS were lost in the transfer to solid media, with all 300 isolates belonging to Proteobacteria, Firmicutes, Actinobacteria or Bacteroidetes, the four phyla most frequently associated with soil culturing efforts. The soils spiked with high diesel fuel concentrations exhibited reduced species richness, diversity and a selection towards heterotrophs and hydrocarbon degraders in comparison to the control soils. Based on these observations and the unusually high level of overlap in microbial taxa observed between methods, we suggest the SSMS holds potential to exploit hydrocarbon degraders and other targets within simplified bacterial systems, yet is inadequate for soil ecology and ecotoxicology studies where identifying rare oligotrophic species is paramount. PMID:27827405

The impact of radiocesium input forms on its extractability in Fukushima forest soils.

PubMed

Teramage, Mengistu T; Carasco, Loic; Orjollet, Daniel; Coppin, Frederic

2018-05-05

The effects of 137 Cs deposit forms on its ageing in soil have not yet been reported. Soluble and Solid 137 Cs input forms were mixed with the mineral soils collected under Fukushima's coniferous and broadleaf forests, incubated under controlled laboratory, and examined the evolution of 137 Cs availability over time. Results show that the extracted 137 Cs fraction with water was less than 1% for the soluble input form and below detection limit for the solid input forms. Likewise, with an acetate reagent, the extracted 137 Cs fraction ranged from 46 to 56% for the soluble input and from 2 to 15% for the solid input, implying that the nature of the 137 Cs contamination strongly influences its extractability and mobility in soil. Although the degradation of organic materials was apparent, its impact on the 137 Cs extractability was found to be weak. Nevertheless, more Ac-available 137 Cs was obtained from broadleaf organic material mixes than the coniferous counterparts, suggesting that the lignified nature of latter tend to retain more 137 Cs. When extrapolated to a field context, more available 137 Cs fraction may be expected from wet-derived contaminated forest soils than contaminated via solid-derived inputs. Such information could be helpful for radioecological management schemes in contaminated forest environments. Copyright © 2018 Elsevier B.V. All rights reserved.

FORMATION OF CHLOROPYROMORPHITE IN A LEAD-CONTAMINATED SOIL AMENDED WITH HYDROXYAPATITE

EPA Science Inventory

To evaluate conversion of soil Pb to pyromorphite, a Pb contaminated soil collected adjacent to a historical smelter was reacted with hydroxyapatite in a traditional incubation experiment and in a dialysis system in which the soil and hydroxyapatite solids were separated by a dia...

Use of mixed solid waste as a soil amendment for saline-sodic soil remediation and oat seedling growth improvement.

PubMed

Fan, Yuan; Ge, Tian; Zheng, Yanli; Li, Hua; Cheng, Fangqin

2016-11-01

Soil salinization has become a worldwide problem that imposes restrictions on crop production and food quality. This study utilizes a soil column experiment to address the potential of using mixed solid waste (vinegar residue, fly ash, and sewage sludge) as soil amendment to ameliorate saline-sodic soil and enhance crop growth. Mixed solid waste with vinegar residue content ranging from 60-90 %, sewage sludge of 8.7-30 %, and fly ash of 1.3-10 % was added to saline-sodic soil (electrical conductivity (EC 1:5 ) = 1.83 dS m -1 , sodium adsorption ratio (SAR 1:5 ) = 129.3 (mmol c L -1 ) 1/2 , pH = 9.73) at rates of 0 (control), 130, 260, and 650 kg ha -1 . Results showed that the application of waste amendment significantly reduced SAR, while increasing soil soluble K + , Ca 2+ , and Mg 2+ , at a dose of 650 kg ha -1 . The wet stability of macro-aggregates (>1 mm) was improved 90.7-133.7 % when the application rate of amendment was greater than 260 kg ha -1 . The application of this amendment significantly reduced soil pH. Germination rates and plant heights of oats were improved with the increasing rate of application. There was a positive correlation between the percentage of vinegar residue and the K/Na ratio in the soil solutions and roots. These findings suggest that applying a mixed waste amendment (vinegar residue, fly ash, and sewage sludge) could be a cost-effective method for the reclamation of saline-sodic soil and the improvement of the growth of salt-tolerant plants.

Linking Environmental Exposure with Public Health: Dichlorodiphenyltrichloroethane Extracted from Soils and Water of Recently Exposed Communities of Selected Locations in Zambia

PubMed Central

Sipilanyambe Munyinda, Nosiku; Michelo, Charles; Sichilongo, Kwenga

2015-01-01

Background. In 2000, a Zambian private mining company reintroduced the use of dichlorodiphenyltrichloroethane (DDT) to control malaria in two districts. From 2000 to 2010, DDT had been applied in homes without any studies conducted to ascertain its fate in the environment. We aimed to quantify the presence of DDT and its metabolites in the soil and water around communities where it was recently used. Methods. We collected superficial soil and water samples from drinking sources of three study areas. DDT was extracted by QuEChERS method and solid phase extraction for soils and water, respectively. Analysis was by gas chromatography-mass spectrometry. A revalidated method with limits of detection ranging from 0.034 to 0.04 ppb was used. Results. Median levels of total DDT were found at 100.4 (IQR 90.9–110) and 725.4 ng/L (IQR 540–774.5) for soils and water, respectively. No DDT above detection limits was detected in the reference area. These results are clinically significant given the persistent characteristics of DDT. Conclusion. DDT presence in these media suggests possible limitations in the environmental safeguards during IRS. Such occurrence could have potential effects on humans, especially children; hence, there is a need to further examine possible associations between this exposure and humans. PMID:26579199

Studying the spatial variability of Cr in agricultural field using both particle induced X-ray emission (PIXE) and instrumental neutron activation analysis (INAA) technique

NASA Astrophysics Data System (ADS)

Cruvinel, Paulo E.; Crestana, Sílvio; Artaxo, Paulo; Martins, JoséV.; Armelin, Maria JoséA.

1996-04-01

In the field of soil physics, a technique which permits a non-destructive, accurate and fast elemental analysis with a minimum of sample preparation effort is often desired. Although trace elements are minor components of the solid phase, they play an important role in soil fertility. Cr is of nutritional importance because it is a required element in human and animal nutrition. The immobility of Cr may be responsible for an inadequate Cr supply to plants. This work not only demonstrates the suitability of PIXE as a fast and non-destructive technique, useful to measure Cr content in soil samples, but also outlines a study of spatial variability of that element in agricultural field. To demonstrate the capability of the method soil samples were collected in a 5000 m 2 agricultural field. The soil samples were analyzed using both PIXE and INAA techniques. Besides, a Fourier interpolation technique was used to verify the distribution of Cr along of the sampled field. INAA was carried out by means of the γ-ray emitted by 51Cr(320 keV). Results show that there is a good linear relationship between the elemental concentration of Cr obtained using those techniques, i.e. a correlation coefficient of r2 = 0.82 was achieved.

Natural attenuation processes for remediation of arsenic contaminated soils and groundwater.

PubMed

Wang, Suiling; Mulligan, Catherine N

2006-12-01

Arsenic (As) contamination presents a hazard in many countries. Natural attenuation (NA) of As-contaminated soils and groundwater may be a cost-effective in situ remedial option. It relies on the site intrinsic assimilative capacity and allows in-place cleanup. Sorption to solid phases is the principal mechanism immobilizing As in soils and removing it from groundwater. Hydroxides of iron, aluminum and manganese, clay and sulfide minerals, and natural organic matter are commonly associated with soils and aquifer sediments, and have been shown to be significant As adsorbents. The extent of sorption is influenced by As speciation and the site geochemical conditions such as pH, redox potential, and the co-occurring ions. Microbial activity may catalyze the transformation of As species, or mediate redox reactions thus influencing As mobility. Plants that are capable of hyperaccumulating As may translocate As from contaminated soils and groundwater to their tissues, providing the basis for phytoremediation. However, NA is subject to hydrological changes and may take substantial periods of time, thus requiring long-term monitoring. The current understanding of As NA processes remains limited. Sufficient site characterization is critical to the success of NA. Further research is required to develop conceptual and mathematical models to predict the fate and transport of As and to evaluate the site NA capacity. Engineering enhanced NA using environmentally benign products may be an effective alternative.

LS3MIP (v1.0) Contribution to CMIP6: The Land Surface, Snow and Soil Moisture Model Intercomparison Project Aims, Setup and Expected Outcome.

NASA Technical Reports Server (NTRS)

Van Den Hurk, Bart; Kim, Hyungjun; Krinner, Gerhard; Seneviratne, Sonia I.; Derksen, Chris; Oki, Taikan; Douville, Herve; Colin, Jeanne; Ducharne, Agnes; Cheruy, Frederique;

Rapid and effective decontamination of chlorophenol-contaminated soil by sorption into commercial polymers: concept demonstration and process modeling.

PubMed

Tomei, M Concetta; Mosca Angelucci, Domenica; Ademollo, Nicoletta; Daugulis, Andrew J

2015-03-01

Solid phase extraction performed with commercial polymer beads to treat soil contaminated by chlorophenols (4-chlorophenol, 2,4-dichlorophenol and pentachlorophenol) as single compounds and in a mixture has been investigated in this study. Soil-water-polymer partition tests were conducted to determine the relative affinities of single compounds in soil-water and polymer-water pairs. Subsequent soil extraction tests were performed with Hytrel 8206, the polymer showing the highest affinity for the tested chlorophenols. Factors that were examined were polymer type, moisture content, and contamination level. Increased moisture content (up to 100%) improved the extraction efficiency for all three compounds. Extraction tests at this upper level of moisture content showed removal efficiencies ≥70% for all the compounds and their ternary mixture, for 24 h of contact time, which is in contrast to the weeks and months, normally required for conventional ex situ remediation processes. A dynamic model characterizing the rate and extent of decontamination was also formulated, calibrated and validated with the experimental data. The proposed model, based on the simplified approach of "lumped parameters" for the mass transfer coefficients, provided very good predictions of the experimental data for the absorptive removal of contaminants from soil at different individual solute levels. Parameters evaluated from calibration by fitting of single compound data, have been successfully applied to predict mixture data, with differences between experimental and predicted data in all cases being ≤3%. Copyright © 2014 Elsevier Ltd. All rights reserved.

Solubility of aluminum and silica in Spodic horizons as affected by drying and freezing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simonsson, M.; Berggren, D.; Gustafsson, J.P.

The release of toxic Al{sup 3+} is one of the most serious consequences of anthropogenic soil acidification. Therefore, the mechanisms controlling Al solubility have been a topic of intense research for more than a decade. For convenience, soil samples are often dried before storage and experimental use. However, the literature offers examples of drying that results in changes in pH, solubility of organic matter, and dissolution rates of Al. In this study, the authors examined the solubility of Al and Si in fresh soil and in soil that had been dried or deep-frozen. Five Spodosol B horizon soils were subjectedmore » to batch titrations, where portions of each soil were equilibrated with solutions with varying concentrations of acid or base added. Extractions with acid oxalate and Na pyrophosphate indicated the presence of imogolite-type materials (ITM) in three of the soils. In the other two soils most secondary solid-phase Al was associated with humic substances. Deep-freezing did not significantly change pH nor the concentration of Al or Si as compared with fresh soil. Drying, on the other hand, yielded pH increases of up to 0.3 units at a given addition of acid or base, whereas Al{sup 3+} changed only slightly, implying a higher Al solubility in all of the soils. Furthermore, dissolved silica increased by up to 200% after drying, except in a soil that almost completely lacked oxalate-extractable Si. The authors suggest that drying enhanced the dissolution of ITM by disrupting soil organic matter, thus exposing formerly coated mineral surfaces. In the soil where dissolved Si did not change with drying, it has been demonstrated that Al-humus complexes controlled Al solubility. They suggest that fissures in the organic material caused by drying may have exposed formerly occluded binding sites that had a higher Al saturation than had sites at the surface of humus particles.« less

Assessment of a sequential extraction protocol by examining solution chemistry and mineralogical evolution

NASA Astrophysics Data System (ADS)

Maubec, Nicolas; Pauwels, Hélène; Noël, Hervé; Bourrat, Xavier

2015-04-01

Knowledge of the behavior of heavy metals, such as copper and zinc in sediments, is a key factor to improve the management of rivers. The mobility of these metals, which may be harmful to the environment, depends directly on their concentration and speciation , which in turn depend on physico-chemical parameters such as mineralogy of the sediment fraction, pH, redox potential, salinity etc ... (Anderson et al., 2000; Sterckeman et al., 2004; Van Oort et al., 2008). Several methods based on chemical extractions are currently applied to assess the behavior of heavy metals in soils and sediments. Among them, sequential extraction procedure is widely used in soil and sediment science and provides details about the origin, biological and physicochemical availability, mobilization and transports of trace metals elements. It is based on the use of a series of extracting reagents to extract selectively heavy metals according to their association within the solid phase (Cornu and Clozel, 2000) including the following different fraction : exchangeable, bound to carbonates, associated to oxides (reducible fraction), linked to organic matter and sulfides (oxidizable fraction) as well as silicate minerals so called residual fraction (Hickey and Kittrick, 1984; Tessier et al., 1979). Consequently sequential extraction method is expected to simulate a lot of potential natural and anthropogenic modifications of environmental conditions (Arey et al., 1999; Brannon and Patrick, 1987; Hickey and Kittrick, 1984; La Force et al., 1999; Tessier et al., 1979). For three decades, a large number of protocols has been proposed, characterized by specific reagents and experimental conditions (concentrations, number of steps, extraction orders and solid/solution ratio) (Das et al., 1995; Gomez Ariza et al., 2000; Quevauviller et al., 1994; Rauret, 1998; Tack and Verloo, 1995), but it appeared that several of them suffer from a lack of selectivity of applied reagents: besides target ones, some of them are able to leach several solid phases. In this context, the aim of the present study is to investigate the effectiveness and the selectivity of different reagents for metal extraction from target geochemical fraction. It is based on solid analyses with the use of X-ray diffraction and a scanning electron microscopy (SEM) coupled to a microRaman spectrometer in conjunction with chemical analyses of extracting solutions at each step. This methodology provides the opportunity to assess more accurately the effect of each reagent. The study focuses on extraction of Cu and Zn from sediment samples collected at two sites from river banks and characterized by presence of Quartz, Feldspar K, Micas, Kaolinite but with differences regarding accessory phases (pyrite, organic matter, iron oxy- hydroxide, calcite). The interaction of the samples with eight different reagents was assessed and compared (Ca(NO3)2 and CaCl2 for the exchangeable fraction; buffered solutions of sodium acetate/acetic acid at pH = 5.5 and pH = 5 for the acido-soluble fraction; hydroxylamine hydrochloride and a solution of ammonium oxalate/oxalic acid for reducible fraction; hydrogen peroxide and sodium hypochlorite for the oxidizable fraction. In-depth characterization of solid residue at each step allowed proposing the best protocol for both metals. Anderson, P., Davidson, C. M., Duncan, A. L., Littlejohn, D., Ure, A. M., and Garden, L. M. (2000). Column leaching and sorption experiments to assess the mobility of potentially toxic elements in industrially contaminated land. Journal of Environmental Monitoring, 2. Arey, J. S., Seaman, J. C., and Bertsch, P. M. (1999). Immobilization of uranium in contaminated sediments by hydroxyapatite addition. Environmental Science & Technology, 33, 337-342. Brannon, J. M., and Patrick, W. H. (1987). Fixation, transformation, and mobilization of arsenic in sediments.Environmental Science & Technology, 21, 450-459. Cornu, S., and Clozel, B. (2000). Extractions séquentielles et spéciation des éléments trace métalliques dans les sols naturels. Analyse critique. 7, 179-189. Das, A. K., Chakraborty, R., Cervera, M. L., and Delaguardia, M. (1995). Metal speciation in solid matrices. Talanta, 42. Gomez Ariza, J. L., Giraldez, I., Sanchez-Rodas, D., and Morales, E. (2000). Selectivity assessment of a sequential extraction procedure for metal mobility characterization using model phases. Talanta, 52, 545-554. Hickey, M. G., and Kittrick, J. A. (1984). Chemical partitioning of cadmium, copper, nickel and zinc in soils and sediments containing high-levels of heavy metals. Journal of Environmental Quality, 13, 372-376. La Force, M. J., Fendorf, S., Li, G. C., and Rosenzweig, R. F. (1999). Redistribution of trace elements from contaminated sediments of Lake Coeur d'Alene during oxygenation. Journal of Environmental Quality, 28, 1195-1200. Quevauviller, P., Rauret, G., Muntau, H., Ure, A. M., Rubio, R., Lopezsanchez, J. F., Fiedler, H. D., and Griepink, B. (1994). Evaluation of a sequential extraction procedure for the determination of extractable trace-metal contents in sediments. Fresenius Journal of Analytical Chemistry, 349. Rauret, G. (1998). Extraction procedures for the determination of heavy metals in contaminated soil and sediment. Talanta, 46(3), 449-455. Sterckeman, T., Douay, F., Baize, D., Fourrier, H., Proix, N., and Schvartz, C. (2004). Factors affecting trace element concentrations in soils developed on recent marine deposits from northern France. Applied Geochemistry, 19. Tack, F. M. G., and Verloo, M. G. (1995). Chemical speciation and fraéctination in soil and sediment heavy-metal analysis - a review. International Journal of Environmental Analytical Chemistry, 59, 225-238. Tessier, A., Campbell, P. G. C., and Bisson, M. (1979). Sequential extraction procedure for the speciation of particulate trace-metals. Analytical Chemistry, 51. Van Oort, F., Jongmans, A. G., Lamy, I., Baize, D., and Chevallier, P. (2008). Impacts of long-term waste-water irrigation on the development of sandy Luvisols: consequences for metal pollutant distributions. European Journal of Soil Science, 59.

Effects of biochars produced from solid organic municipal waste on soil quality parameters

USDA-ARS?s Scientific Manuscript database

New, value-added uses for solid organic waste are needed for environmental and economic sustainability. Fortunately, value-added biochars can be produced from mixed organic solid waste, thereby addressing solid waste management issues, and enabling long-term carbon sequestration. We hypothesize that...

Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.

2017-12-01

At the extremely low temperatures in Titan's upper troposphere and on Pluto's surface, the atmospheres as a whole are subject to freeze into solid solutions, not pure ices. The presence of the solid phases introduces conditions with rich phase equilibria upon seasonal changes, even if the temperature undergoes only small changes. For the first time, the profile of atmospheric methane in Titan's troposphere will be reproduced complete with the solid solutions. This means that the freezing point, i.e. the altitude where the first solid phase appears, is determined. The seasonal change will also be evaluated both at the equator and the northern polar region. For Pluto, also for the first time, the seasonal solid-vapor equilibria will be evaluated. The fate of the two solid phases, the methane-rich and carbon-monoxide-rich solid solutions, will be analyzed upon temperature and pressure changes. Such investigations are enabled by the development of a molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, which includes solid solutions in its phase-equilibria calculations. The atmospheres of Titan and Pluto are modeled as ternary gas mixtures: nitrogen-methane-ethane and nitrogen-methane-carbon monoxide, respectively. Calculations using CRYOCHEM can provide us with compositions not only in two-phase equilibria, but also that in three-phase equilibria. Densities of all phases involved will also be calculated. For Titan, density inversion between liquid and solid phases will be identified and presented. In the inversion, the density of solid phase is less than that in the liquid phase. The method and results of this work will be useful for further investigations and modeling on the atmospheres of Titan, Pluto, and other bodies with similar conditions in the Solar System and beyond.

[Determination of myclobutanil 25% WG degradation dynamics in ginseng root, stem, leaf and soil by HPLC-MS/MS].

PubMed

Wang, Yan; Wang, Chun-Wei; Gao, Jie; Cui, Li-Li; Xu, Yun-Cheng

2014-07-01

A high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) method was developed for determining degradation dynamics and final residues of myclobutanil 25% WG in ginseng root, stem, leaf and soil. The samples were extracted with acetonitrile, cleaned-up with primary secondary amine (PSA) solid phase extraction cartridge, separated by Kromasil Eternity-5-C18 (2.1 mm x 150 mm, 5 microm) column with a gradient of acetonitrile and 0.1% formate in water as mobile phases, and analyzed with the multiple reaction monitoring (MRM) in positive ion mode by employing the external standard method. The average recoveries and the relative standard derivations (RSDs) of myclobutanil at the spiked level of 0.01-0.20 mg x kg(-1) were 80.9%-90.7% and 5.54%-9.29%, respectively, and the limit of quantification (LOQ) was 0.005 mg x kg(-1). The method with good reproducible, high precision and low detection limit could meet the requirements of residual analysis on ginseng production. The half-lives of myclobutanil were from 6.25 days to 9.94 days in ginseng root, stem, leaf and soil at spraying dosage of 1 152 g x hm(-2) The final residues were below 0.060 1 mg x kg(-1) in root, below 0.081 7 mg x kg(-1) in stem, 0.006 0-0.102 2 mg x kg(-1) in leaf and below 0.037 6 mg x kg(-1) in soil at spraying dosage range from 576 to 1 152 g x hm(-2). It is recommended that the MRLs of myclobutanil in dried ginseng may be suggested to be 0.10 mg x kg(-1) temporarily, and the preharvest interval was set at 35 days.

Influence of solid-liquid separation method parameters employed in soil leaching tests on apparent metal concentration.

PubMed

Imoto, Yukari; Yasutaka, Tetsuo; Someya, Masayuki; Higashino, Kazuo

2018-05-15

Soil leaching tests are commonly used to evaluate the leachability of hazardous materials, such as heavy metals, from the soil. Batch leaching tests often enhance soil colloidal mobility and may require solid-liquid separation procedures to remove excess soil particles. However, batch leaching test results depend on particles that can pass through a 0.45μm membrane filter and are influenced by test parameters such as centrifugal intensity and filtration volume per filter. To evaluate these parameters, we conducted batch leaching experiments using metal-contaminated soils and focused on the centrifugal intensity and filtration volume per filter used in solid-liquid separation methods currently employed in standard leaching tests. Our experiments showed that both centrifugal intensity and filtration volume per filter affected the reproducibility of batch leaching tests for some soil types. The results demonstrated that metal concentrations in the filtrates significantly differed according to the centrifugal intensity when it was 3000 g for 2h or less. Increased filtration volume per filter led to significant decreases in filtrate metal concentrations when filter cakes formed during filtration. Comparison of the filtration tests using 0.10 and 0.45μm membrane filters showed statistically significant differences in turbidity and metal concentration. These findings suggest that colloidal particles were not adequately removed from the extract and contributed substantially to the apparent metal concentrations in the leaching test of soil containing colloidal metals. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Rheological properties of soil: a review

NASA Astrophysics Data System (ADS)

Zhu, Guangli; Zhu, Long; Yu, Chao

2017-05-01

Recently rheological methods have been applied to investigate the mechanical properties of soil micro-structure. Rheological techniques have a number of quantitative physically based measurements and offer a better understanding of how soil micro-structure behaves when subject to stress. Rheological material is refers to deformation properties similar to the solid and flow properties similar to the liquid of bound water and colloidal substances under stress. Soil rheology is divided into fluid rheology and plasticity rheology. Fluid rheology is produced by rheological material. Plasticity rheology mainly refers to the sliding and peristaltic between soil solid particles under shear stress. It is generally believed that the soft soil rheology mainly belongs to fluid rheology, while the rheology of sand and other coarse grained soil mainly belongs to plasticity rheology. Thus, rheology mechanisms of soft soil and sand are different. This paper introduces the methods of the research progress on the rheology of soil, in the soil rheological mechanism, rheological model and rheological numerical aspects of the research at home and abroad were summarized and analysed, discussed the problems existed in related research, and puts forward some suggestions for the future study on the rheology of soil.

Temporal soil bulk density following tillage

USDA-ARS?s Scientific Manuscript database

Soil is the medium for air, energy, water, and chemical transport between the atmosphere and the solid earth. Soil bulk density is a key variable impacting the rate at which this transport occurs. Typically, soil bulk density is measured by the gravimetric method, where a sample of known volume is t...

Molecular aspects of aromatic C additions to soils: Implications of biochar quality for ecosystem functionality

EPA Science Inventory

Solid residues of incomplete combustion (biochar or char) are continuously being added to soils due to natural vegetation fires in many ecosystems. However, new strategies for carbon sequestration in soils are likely to include the active addition of biochar to soils. Since bioc...

Surfactant and Irrigation Effects on Runoff, Erosion, and Water Retention of Three Wettable Soils

USDA-ARS?s Scientific Manuscript database

Surfactants are chemical compounds that change the contact angle of water on solid surfaces and are commonly used to increase infiltration into hydrophobic soil. Since production fields with water-repellent soil often contain areas of wettable soil, surfactants applied to such fields will likely be ...

Surfactant and irrigation effects on wettable soils: Runoff, erosion, and water retention responses

USDA-ARS?s Scientific Manuscript database

Surfactants are chemical compounds that change the contact angle of water on solid surfaces and are commonly used to increase infiltration into hydrophobic soil. Since production fields with water-repellent soil often contain areas of wettable soil, surfactants applied to such fields will likely be ...

Materials research for passive solar systems: Solid-state phase-change materials

NASA Astrophysics Data System (ADS)

Benson, D. K.; Webb, J. D.; Burrows, R. W.; McFadden, J. D. O.; Christensen, C.

1985-03-01

A set of solid-state phase-change materials is being evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol (C5H12O4), pentaglycerinve (C5H12O3), and neopentyl glycol (C5H12O2). Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature between 25 C and 188 C, and have latent heats of transformation etween 20 and 70 cal/g. Transformation temperatures, specific heats, and latent heats of transformation have been measured for a number of these materials. Limited cyclic experiments suggest that the solid solutions are stable. These phase-change materials exhibit large amounts of undercooling; however, the addition of certain nucleating agents as particulate dispersions in the solid phase-change material greatly reduces this effect. Computer simulations suggest that the use of an optimized solid-state phase-change material in a Trombe wall could provide better performance than a concrete Trombe wall four times thicker and nine times heavier.

Fire impact on forest soils evaluated using near-infrared spectroscopy and multivariate calibration.

PubMed

Vergnoux, A; Dupuy, N; Guiliano, M; Vennetier, M; Théraulaz, F; Doumenq, P

2009-11-15

The assessment of physico-chemical properties in forest soils affected by fires was evaluated using near infrared reflectance (NIR) spectroscopy coupled with chemometric methods. In order to describe the soil properties, measurements were taken of the total organic carbon on solid phase, the total nitrogen content, the organic carbon and the specific absorbences at 254 and 280 nm of humic substances, organic carbon in humic and fulvic acids, concentrations of NH(4)(+), Ca(2+), Mg(2+), K(+) and phosphorus in addition to NIR spectra. Then, a fire recurrence index was defined and calculated according to the different fires extents affecting soils. This calculation includes the occurrence of fires as well as the time elapsed since the last fire. This study shows that NIR spectroscopy could be considered as a tool for soil monitoring, particularly for the quantitative prediction of the total organic carbon, total nitrogen content, organic carbon in humic substances, concentrations of phosphorus, Mg(2+), Ca(2+) and NH(4)(+) and humic substances UVSA(254). Further validation in this field is necessary however, to try and make successful predictions of K(+), organic carbon in humic and fulvic acids and the humic substances UVSA(280). Moreover, NIR coupled with PLS can also be useful to predict the fire recurrence index in order to determine the spatial variability. Also this method can be used to map more or less burned areas and possibly to apply adequate rehabilitation techniques, like soil litter reconstitution with organic enrichments (industrial composts) or reforestation. Finally, the proposed recurrence index can be considered representative of the state of the soils.

Spatial distributions and seasonal variations of organochlorine pesticides in water and soil samples in Bolu, Turkey.

PubMed

Karadeniz, Hatice; Yenisoy-Karakaş, Serpil

2015-03-01

In this study, a total of 75 water samples (38 groundwater and 37 surface water samples) and 54 surface soil samples were collected from the five districts of Bolu, which is located in the Western Black Sea Region of Turkey in the summer season of 2009. In the autumn season, 17 water samples (surface water and groundwater samples) and 17 soil samples were collected within the city center to observe the seasonal changes of organochlorine pesticides (OCPs). Groundwater and surface water samples were extracted using solid phase extraction. Soil samples were extracted ultrasonically. Sixteen OCP compounds in the standard solution were detected by a gas chromatography-electron capture detector (GC-ECD). Therefore, the method validation was performed for those 16 OCP compounds. However, 13 OCP compounds could be observed in the samples. The concentrations of most OCPs were higher in samples collected in the summer than those in the autumn. The most frequently observed pesticides were endosulfan sulfate and 4,4'-dichlorodiphenyltrichloroethane (DDT) in groundwater samples, α-HCH in surface water samples, and endosulfan sulfate in soil samples. The average concentration of endosulfan sulfate was the highest in water and soil samples. Compared to the literature values, the average concentrations in this study were lower values. Spatial distribution of OCPs was evaluated with the aid of contour maps for the five districts of Bolu. Generally, agricultural processes affected the water and soil quality in the region. However, non-agricultural areas were also affected by pesticides. The concentrations of pesticides were below the legal limits of European directives for each pesticide.

Pressure and Chemical Potential: Effects Hydrophilic Soils Have on Adsorption and Transport

NASA Astrophysics Data System (ADS)

Bennethum, L. S.; Weinstein, T.

2003-12-01

Using the assumption that thermodynamic properties of fluid is affected by its proximity to the solid phase, a theoretical model has been developed based on upscaling and fundamental thermodynamic principles (termed Hybrid Mixture Theory). The theory indicates that Darcy's law and the Darcy-scale chemical potential (which determines the rate of adsorption and diffusion) need to be modified in order to apply to soils containing hydrophilic soils. In this talk we examine the Darcy-scale definition of pressure and chemical potential, especially as it applies to hydrophilic soils. To arrive at our model, we used hybrid mixture theory - first pioneered by Hassanizadeh and Gray in 1979. The technique involves averaging the field equations (i.e. conservation of mass, momentum balance, energy balance, etc.) to obtain macroscopic field equations, where each field variable is defined precisely in terms of its microscale counterpart. To close the system consistently with classical thermodynamics, the entropy inequality is exploited in the sense of Coleman and Noll. With the exceptions that the macroscale field variables are defined precisely in terms of their microscale counterparts and that microscopic interfacial equations can also be treated in a similar manner, the resulting system of equations is consistent with those derived using classical mixture theory. Hence the terminology, Hybrid Mixture Theory.

Matrix-specific distribution and diastereomeric profiles of hexabromocyclododecane (HBCD) in a multimedia environment: Air, soil, sludge, sediment, and fish.

PubMed

Jo, Hyeyeong; Son, Min-Hui; Seo, Sung-Hee; Chang, Yoon-Seok

2017-07-01

Hexabromocyclododecane (HBCD) contamination and its diastereomeric profile were investigated in a multi-media environment along a river at the local scale in air, soil, sludge, sediment, and fish samples. The spatial distribution of HBCD in each matrix showed a different result. The highest concentrations of HBCD in air and soil were detected near a general industrial complex; in the sediment and sludge samples, they were detected in the down-stream region (i.e., urban area). Each matrix showed the specific distribution patterns of HBCD diastereomers, suggesting continuous inputs of contaminants, different physicochemical properties, or isomerizations. The particle phases in air, sludge, and fish matrices were dominated by α-HBCD, owing to HBCD's various isomerization processes and different degradation rate in the environment, and metabolic capabilities of the fish; in contrast, the sediment and soil matrices were dominated by γ-HBCD because of the major composition of the technical mixtures and the strong adsorption onto solid particles. Based on these results, the prevalent and matrix-specific distribution of HBCD diastereomers suggested that more careful consideration should be given to the characteristics of the matrices and their effects on the potential influence of HBCD at the diastereomeric level. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessment of the biological and chemical availability of the freshly spiked and aged DDE in soil.

PubMed

Škulcová, L; Neuwirthová, N; Hofman, J; Bielská, L

2016-05-01

The study compared the ability of various chemical methods (XAD, β-hydroxypropylcyclodextrin - HPCD) and solid phase micro-extraction (SPME)) to mimic earthworm uptake from two similar soils containing either spiked or aged p,p´-DDE, thus representing two extreme scenarios with regard to the length of pollutant-soil contact time and the way of contamination. The extent of bioaccumulation was assessed at fixed exposure periods (10 and 21 days) and at equilibrium derived from uptake curves by multiple-point comparison or kinetic modeling. The decision on the best chemical predictor of biological uptake differed. The degree of bioaccumulation at equilibrium was best predicted by XAD while HPCD rather reflected the extent of accumulation derived after 21 days when, however, steady-state was not reached for spiked p,p´-DDE. SPME seemed to underestimate the uptake of aged p,p´-DDE, probably of the fraction taken up via soil particles. Thus, the degree of predictability seems to be associated with the capability of the chemical method to mimic the complex earthworm uptake via skin and intestinal tract as well as with the quality of biological data where the insufficient length of exposure period appears to be the major concern. Copyright © 2016 Elsevier Ltd. All rights reserved.

Developing a Planting Medium from Solid Waste Compost and Construction and Demolition Rubble for Use in Quarry Rehabilitation

NASA Astrophysics Data System (ADS)

Assaf, E. A.

2015-12-01

The combination of construction, demolition and excavation (CDE) waste along with the increase in solid waste generation has put a major stress on Lebanon and on the management of its solid waste. Compounding this problem are the issues of quarries closure and rehabilitation and a decrease in forest and vegetative cover. This research aims to provide an integrated solution to the stated problem by developing a "soil mix" derived from a mélange of the organic matter of the solid waste (compost), the CDE waste, and soil. Excavation and construction debris were ground to several sizes and mixed with compost and soil at different ratios. Replicates of these mixes and a set of control (regular soil) were used. In this mix, native and indicator plants are planted (in pots). The plant species used are Mathiolla crassifolia and Zea mays (Corn). Results have shown successful growth of both corn and Mathiolla seedlings in the mixes with higher amounts of construction rubble and compost i.e. Rubble: Soil: Compost Ratio of 2:1:1 and 1:0:1. However treatments with no compost and with less quantities of rubble demonstrated the inability of the soil used to sustain plant growth alone (1:1:1 and 1:1:0). Last but not least, the control consisting of soil only ended up being the weakest mix with yellow corn leaves and small Mathiolla seedlings fifty days after planting and fertilizing. Additionally, soil analysis, rubble and compost analysis were conducted. The samples were tested for heavy metals, nutrient availability and values of pH and EC. No contamination has been reported and an abundance of macronutrients and micronutrients was documented for the soil and compost. High alkalinity is due to the presence of concrete and the high percentage of Calcium Carbonate in Lebanese soils. Accordingly, the most adequate mixes for planting are treatments A (2:1:1) and B (1:0:1) and they should be pursued for a pilot scale study to test their potential use in quarry rehabilitation and eventually urban agriculture.

The influence of traffic vibrations on the radon potential.

PubMed

Schmid, S; Wiegand, J

1998-02-01

The influence of traffic vibrations on the radon potential is analyzed in this study. Generally, the radon concentration in soil-gas increases through traffic vibrations. The influence of the vibrations is determined near railway tracks and heavy-traffic roads. Soils above natural, in-place, bedrock (solid and unconsolidated rocks) and backfills were studied. The type of vibrations, as well the soil material, have a pronounced influence on the amount of increase of the radon concentration. The spatial radius of influence is wider with railway traffic (>30 m) than with motor vehicle traffic (<25 m). Close to the traffic lanes the increase of the radon concentration by motor vehicle traffic is significantly higher (37%) than that by railway traffic (11.5%). There are no differences between locations, which lay above unconsolidated rock (11.1%), and locations above solid rock (11.8%). In addition to the increased radon concentrations, the averaged radon concentration decreases with increasing distance to the vibration source, but only at locations that lay above solid rock. Both phenomena can be explained by a "pump effect": the mechanical vibration of soil and mineral particles leads to an upward motion of the whole volume of soil-gas. During the vibrations the topmost soil layers lose radon to the atmosphere and as a result the upward transport is increased.

Benzocaine polymorphism: pressure-temperature phase diagram involving forms II and III.

PubMed

Gana, Inès; Barrio, Maria; Do, Bernard; Tamarit, Josep-Lluís; Céolin, René; Rietveld, Ivo B

2013-11-18

Understanding the phase behavior of an active pharmaceutical ingredient in a drug formulation is required to avoid the occurrence of sudden phase changes resulting in decrease of bioavailability in a marketed product. Benzocaine is known to possess three crystalline polymorphs, but their stability hierarchy has so far not been determined. A topological method and direct calorimetric measurements under pressure have been used to construct the topological pressure-temperature diagram of the phase relationships between the solid phases II and III, the liquid, and the vapor phase. In the process, the transition temperature between solid phases III and II and its enthalpy change have been determined. Solid phase II, which has the highest melting point, is the more stable phase under ambient conditions in this phase diagram. Surprisingly, solid phase I has not been observed during the study, even though the scarce literature data on its thermal behavior appear to indicate that it might be the most stable one of the three solid phases. Copyright © 2013 Elsevier B.V. All rights reserved.

Hydrogen generation via anaerobic fermentation of paper mill wastes.

PubMed

Valdez-Vazquez, Idania; Sparling, Richard; Risbey, Derek; Rinderknecht-Seijas, Noemi; Poggi-Varaldo, Héctor M

2005-11-01

The objective of this work was to determine the hydrogen production from paper mill wastes using microbial consortia of solid substrate anaerobic digesters. Inocula from mesophilic, continuous solid substrate anaerobic digestion (SSAD) reactors were transferred to small lab scale, batch reactors. Milled paper (used as a surrogate paper waste) was added as substrate and acetylene or 2-bromoethanesulfonate (BES) was spiked for methanogenesis inhibition. In the first phase of experiments it was found that acetylene at 1% v/v in the headspace was as effective as BES in inhibiting methanogenic activity. Hydrogen gas accumulated in the headspace of the bottles, reaching a plateau. Similar final hydrogen concentrations were obtained for reactors spiked with acetylene and BES. In the second phase of tests the headspace of the batch reactors was flushed with nitrogen gas after the first plateau of hydrogen was reached, and subsequently incubated, with no further addition of inhibitor nor substrate. It was found that hydrogen production resumed and reached a second plateau, although somewhat lower than the first one. This procedure was repeated a third time and an additional amount of hydrogen was obtained. The plateaux and initial rates of hydrogen accumulation decreased in each subsequent incubation cycle. The total cumulative hydrogen harvested in the three cycles was much higher (approx. double) than in the first cycle alone. We coined this procedure as IV-SSAH (intermittently vented solid substrate anaerobic hydrogen generation). Our results point out to a feasible strategy for obtaining higher hydrogen yields from the fermentation of industrial solid wastes, and a possible combination of waste treatment processes consisting of a first stage IV-SSAH followed by a second SSAD stage. Useful products of this approach would be hydrogen, organic acids or methane, and anaerobic digestates that could be used as soil amenders after post-treatment.

Fresh organic matter of municipal solid waste enhances phytoextraction of heavy metals from contaminated soil.

PubMed

Salati, S; Quadri, G; Tambone, F; Adani, F

2010-05-01

In this study, the ability of the organic fraction of municipal solid wastes (OFMSW) to enhance heavy metal uptake of maize shoots compared with ethylenediamine disuccinic acid (EDDS) was tested on soil contaminated with heavy metals. Soils treated with OFMSW and EDDS significantly increased the concentration of heavy metals in maize shoots (increments of 302%, 66%, 184%, 169%, and 23% for Cr, Cu, Ni, Zn, and Pb with respect to the control and increments of 933%, 482%, 928%, 428%, and 5551% for soils treated with OFMSW and EDDS, respectively). In soil treated with OFMSW, metal uptake was favored because of the high presence of dissolved organic matter (DOM) (41.6x than soil control) that exhibited ligand properties because of the high presence of carboxylic acids. Because of the toxic effect of EDDS on maize plants, soil treated with OFMSW achieved the highest extraction of total heavy metals. Copyright 2009 Elsevier Ltd. All rights reserved.

The global phase diagram of the Gay-Berne model

NASA Astrophysics Data System (ADS)

de Miguel, Enrique; Vega, Carlos

2002-10-01

The phase diagram of the Gay-Berne model with anisotropy parameters κ=3, κ'=5 has been evaluated by means of computer simulations. For a number of temperatures, NPT simulations were performed for the solid phase leading to the determination of the free energy of the solid at a reference density. Using the equation of state and free energies of the isotropic and nematic phases available in the existing literature the fluid-solid equilibrium was calculated for the temperatures selected. Taking these fluid-solid equilibrium results as the starting points, the fluid-solid equilibrium curve was determined for a wide range of temperatures using Gibbs-Duhem integration. At high temperatures the sequence of phases encountered on compression is isotropic to nematic, and then nematic to solid. For reduced temperatures below T=0.85 the sequence is from the isotropic phase directly to the solid state. In view of this we locate the isotropic-nematic-solid triple point at TINS=0.85. The present results suggest that the high-density phase designated smectic B in previous simulations of the model is in fact a molecular solid and not a smectic liquid crystal. It seems that no thermodynamically stable smectic phase appears for the Gay-Berne model with the choice of parameters used in this work. We locate the vapor-isotropic liquid-solid triple point at a temperature TVIS=0.445. Considering that the critical temperatures is Tc=0.473, the Gay-Berne model used in this work presents vapor-liquid separation over a rather narrow range of temperatures. It is suggested that the strong lateral attractive interactions present in the Gay-Berne model stabilizes the layers found in the solid phase. The large stability of the solid phase, particularly at low temperatures, would explain the unexpectedly small liquid range observed in the vapor-liquid region.

Biochar from Biosolids Pyrolysis: A Review.

PubMed

Paz-Ferreiro, Jorge; Nieto, Aurora; Méndez, Ana; Askeland, Matthew Peter James; Gascó, Gabriel

2018-05-10

Ever increasing volumes of biosolids (treated sewage sludge) are being produced by municipal wastewater facilities. This is a consequence of the continued expansion of urban areas, which in turn require the commissioning of new treatment plants or upgrades to existing facilities. Biosolids contain nutrients and energy which can be used in agriculture or waste-to-energy processes. Biosolids have been disposed of in landfills, but there is an increasing pressure from regulators to phase out landfilling. This article performs a critical review on options for the management of biosolids with a focus on pyrolysis and the application of the solid fraction of pyrolysis (biochar) into soil.

Biochar from Biosolids Pyrolysis: A Review

PubMed Central

Nieto, Aurora; Méndez, Ana; Askeland, Matthew Peter James; Gascó, Gabriel

2018-01-01

Ever increasing volumes of biosolids (treated sewage sludge) are being produced by municipal wastewater facilities. This is a consequence of the continued expansion of urban areas, which in turn require the commissioning of new treatment plants or upgrades to existing facilities. Biosolids contain nutrients and energy which can be used in agriculture or waste-to-energy processes. Biosolids have been disposed of in landfills, but there is an increasing pressure from regulators to phase out landfilling. This article performs a critical review on options for the management of biosolids with a focus on pyrolysis and the application of the solid fraction of pyrolysis (biochar) into soil. PMID:29748488

Soil solid-phase controls lead activity in soil solution.

PubMed

Badawy, S H; Helal, M I D; Chaudri, A M; Lawlor, K; McGrath, S P

2002-01-01

Lead pollution of the environment is synonymous with civilization. It has no known biological function, and is naturally present in soil, but its presence in food crops is deemed undesirable. The concern regarding Pb is mostly due to chronic human and animal health effects, rather then phytotoxicity. However, not much is known about the chemistry and speciation of Pb in soils. We determined the activity of Pb2+, in near neutral and alkaline soils, representative of alluvial, desertic and calcareous soils of Egypt, using the competitive chelation method. Lead activity ranged from 10(-6.73) to 10(-4.83) M, and was negatively correlated with soil and soil solution pH (R2 = -0.92, P < 0.01 and R2 = -0.89, P < 0.01, respectively). It could be predicted in soil solution from the equation: log(Pb2+) = 9.9 - 2pH. A solubility diagram for the various Pb minerals found in soil was constructed using published thermodynamic data obtained from the literature, and our measured Pb2+ activities compared with this information. The measured Pb2+ activities were undersaturated with regard to the solubility of PbSiO3 in equilibrium with SiO2 (soil). However, they were supersaturated with regard to the solubilities of the Pb carbonate minerals PbCO3 (cerussite) and Pb3(CO3)2(OH)2 in equilibrium with atmospheric CO2 and hydroxide Pb(OH)2. They were also supersaturated with regard to the solubilities of the Pb phosphate minerals Pb3(PO4)2, Pb5(PO4)3OH, and Pb4O(PO4)2 in equilibrium with tricalcium phosphate and CaCO3. The activity of Pb2+ was not regulated by any mineral of known solubility in our soils, but possibly by a mixture of Pb carbonate and phosphate minerals.

Vapor phase elemental sulfur amendment for sequestering mercury in contaminated soil

DOEpatents

Looney, Brian B.; Denham, Miles E.; Jackson, Dennis G.

2014-07-08

The process of treating elemental mercury within the soil is provided by introducing into the soil a heated vapor phase of elemental sulfur. As the vapor phase of elemental sulfur cools, sulfur is precipitated within the soil and then reacts with any elemental mercury thereby producing a reaction product that is less hazardous than elemental mercury.

Extractability of 137Cs in Response to its Input Forms into Fukushima Forest Soils.

NASA Astrophysics Data System (ADS)

Mengistu, T. T.; Carasco, L.; Orjollet, D.; Coppin, F.

2017-12-01

In case of nuclear accidents like Fukushima disaster, the influence of 137Cs depositional forms (soluble and/or solid forms) on mineral soil of forest environment on its availability have not reported yet. Soluble (137Cs tagged ultra-pure water) and solid (137Cs contaminated litter-OL and fragmented litter-OF) input forms were mixed with the mineral soils collected under Fukushima coniferous and broadleaf forests. The mixtures then incubated under controlled laboratory condition to evaluate the extractability of 137Cs in soil over time in the presence of decomposition process through two extracting reagents- water and ammonium acetate. Results show that extracted 137Cs fraction with water was less than 1% for soluble input form and below detection limit for solid input form. On the same way with acetate reagent, the extracted 137Cs fraction ranged from 46 to 56% for soluble input and 2 to 15% for solid input, implying the nature of 137Cs contamination strongly influences the extractability and hence the mobility of 137Cs in soil. Although the degradation rate of the organic materials has been calculated in the range of 0.18 ± 0.1 to 0.24 ± 0.1 y-1, its impact on 137Cs extractability appeared very weak at least within the observation period, probably due to shorter time scale. Concerning the treatments of solid 137Cs input forms through acetate extraction, relatively more 137Cs has been extracted from broadleaf organic materials mixes (BL-OL & BL-OF) than the coniferous counterparts. This probably is due to the fact that the lignified coniferous organic materials (CED-OL & CED-OF) components tend to retain more 137Cs than that of the broadleaf. Generally, by extrapolating these observations in to a field context, one can expect more available 137Cs fraction in forest soil from wet depositional pathways such as throughfall and stemflow than those attached with organic materials like litter (OL) and its eco-processed forms (OF).

Speciation study in the sulfamethoxazole-copper-pH-soil system: implications for retention prediction.

PubMed

Morel, Marie-Christine; Spadini, Lorenzo; Brimo, Khaled; Martins, Jean M F

2014-05-15

Sulfamethoxazole (SMX) is a persistent sulfonamide antibiotic drug used in the veterinary and human medical sectors and is widely detected in natural waters. To better understand the reactive transport of this antibiotic in soil, the speciation of the SMX-Cu(II)-H(+) system in solution and the combined sorption of these components in a natural vineyard soil were investigated by acid-base titrimetry and infrared spectroscopy. Cu(II) is considered to represent a strongly complexing trace element cation (such as Cd(2+), Zn(2+), Pb(2+), Ni(2+), etc.) in comparison to more prevalent but more weakly binding cations (such as Ca(2+) and Mg(2+)). Titrimetric studies showed that, relative to other antibiotics, such as tetracycline, SMX is a weak copper chelating agent and a weak soil sorbent at the soil pH (pH6). However, the sorption of SMX in soil increases strongly (by a factor of 6) in the presence of copper. This finding strongly supports the hypothetical formation of ternary SMX-Cu-soil complexes, especially considering that copper is dominantly sorbed in a state at pH6. The data were successfully modelled with PhreeqC assuming the existence of binary and ternary surface complexes in equilibrium with aqueous Cu, SMX and Cu-SMX complexes. It is thought that other strongly complexing cations present on the surface of reactive organic and mineral soil phases, such as Cd(II), Ni(II), Zn(II), Pb(II), Fe(II/III), Mn(II/IV) and Al(III), affect the solid/solution partitioning of SMX. This study thus suggests that surface-adsorbed cations significantly increase the sorption of SMX. Copyright © 2014 Elsevier B.V. All rights reserved.

Microbial links between sulfate reduction and metal retention in uranium- and heavy metal-contaminated soil.

PubMed

Sitte, Jana; Akob, Denise M; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E; Scheinost, Andreas C; Büchel, Georg; Küsel, Kirsten

2010-05-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the (35)SO(4)(2-) radiotracer method, was restricted to reduced soil horizons with rates of < or =142 +/- 20 nmol cm(-3) day(-1). Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that approximately 80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [(13)C]acetate- and [(13)C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined < or =100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching < or =1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems.

In situ silicone tube microextraction: a new method for undisturbed sampling of root-exuded thiophenes from marigold (Tagetes erecta L.) in soil.

PubMed

Mohney, Brian K; Matz, Tricia; Lamoreaux, Jessica; Wilcox, David S; Gimsing, Anne Louise; Mayer, Philipp; Weidenhamer, Jeffrey D

2009-11-01

The difficulties of monitoring allelochemical concentrations in soil and their dynamics over time have been a major barrier to testing hypotheses of allelopathic effects. Here, we evaluate three diffusive sampling strategies that employ polydimethylsiloxane (PDMS) sorbents to map the spatial distribution and temporal dynamics of root-exuded thiophenes from the African marigold, Tagetes erecta. Solid phase root zone extraction (SPRE) probes constructed by inserting stainless steel wire into PDMS tubing were used to monitor thiophene concentrations at various depths beneath marigolds growing in PVC pipes. PDMS sheets were used to map the distribution of thiophenes beneath marigolds grown in thin glass boxes. Concentrations of the two major marigold thiophenes measured by these two methods were extremely variable in both space and time. Dissection and analysis of roots indicated that distribution of thiophenes in marigold roots also was quite variable. A third approach used 1 m lengths of PDMS microtubing placed in marigold soil for repeated sampling of soil without disturbance of the roots. The two ends of the tubing remained out of the soil so that solvent could be washed through the tubing to collect samples for HPLC analysis. Unlike the other two methods, initial experiments with this approach show more uniformity of response, and suggest that soil concentrations of marigold thiophenes are affected greatly even by minimal disturbance of the soil. Silicone tube microextraction gave a linear response for alpha-terthienyl when maintained in soils spiked with 0-10 ppm of this thiophene. This method, which is experimentally simple and uses inexpensive materials, should be broadly applicable to the measurement of non-polar root exudates, and thus provides a means to test hypotheses about the role of root exudates in plant-plant and other interactions.

Application of biochar to sewage sludge reduces toxicity and improve organisms growth in sewage sludge-amended soil in long term field experiment.

PubMed

Kończak, Magdalena; Oleszczuk, Patryk

2018-06-01

The aim of the present study was to determine changes in the physicochemical properties and toxicity of soil amended with sewage sludge (10t dw /ha) or sewage sludge (10t dw /ha) with biochar addition (2.5, 5 or 10% of sewage sludge). The study was carried out as a field experiment over a period of 18months. Samples for analysis were taken at the beginning of the experiment as well as after 6, 12 and 18months. The study investigated toxicity of the unamended soil, sewage sludge-amended soil and sewage sludge-amended soil with biochar addition towards Folsomia candida (collembolan test) and Lepidium sativum (Phytotoxkit F). Moreover, toxicity of aqueous extracts obtained from the tested soils towards Vibrio fischeri (Microtox®) and Lepidium sativum (elongation test) was determined. The study showed that addition of biochar to the sewage sludge and soil reduced leaching of nutrients (mainly phosphorus and potassium) from the amended soil. Biochar significantly reduced sewage sludge toxicity, exhibiting a stimulating effect on the tested organisms. The stimulating effect of biochar addition to the sewage sludge persisted throughout the entire experiment. Apart from the remediatory character of biochar, this is also evidence of its fertilizing character. In the tests with L. sativum (leachates and solid phase) and V. fischeri (leachates), increasing the rate of biochar in the sewage sludge increased root growth stimulation (L. sativum) and bacteria luminescence (V. fischeri). However, increasing biochar rate decreased F. candida reproduction stimulation, which could have been an effect of reduced nutrient bioavailability due to the biochar. Copyright © 2017 Elsevier B.V. All rights reserved.

A user-friendly modified pore-solid fractal model

PubMed Central

Ding, Dian-yuan; Zhao, Ying; Feng, Hao; Si, Bing-cheng; Hill, Robert Lee

2016-01-01

The primary objective of this study was to evaluate a range of calculation points on water retention curves (WRC) instead of the singularity point at air-entry suction in the pore-solid fractal (PSF) model, which additionally considered the hysteresis effect based on the PSF theory. The modified pore-solid fractal (M-PSF) model was tested using 26 soil samples from Yangling on the Loess Plateau in China and 54 soil samples from the Unsaturated Soil Hydraulic Database. The derivation results showed that the M-PSF model is user-friendly and flexible for a wide range of calculation point options. This model theoretically describes the primary differences between the soil moisture desorption and the adsorption processes by the fractal dimensions. The M-PSF model demonstrated good performance particularly at the calculation points corresponding to the suctions from 100 cm to 1000 cm. Furthermore, the M-PSF model, used the fractal dimension of the particle size distribution, exhibited an accepted performance of WRC predictions for different textured soils when the suction values were ≥100 cm. To fully understand the function of hysteresis in the PSF theory, the role of allowable and accessible pores must be examined. PMID:27996013

Physically-based quantitative analysis of soil erosion induced by heavy rainfall on steep slopes

NASA Astrophysics Data System (ADS)

Della Sala, Maria; Cuomo, Sabatino; Novità, Antonio

2014-05-01

Heavy rainstorms cause either shallow landslides or soil superficial erosion in steep hillslopes covered by coarse unsaturated soils (Cascini et al., 2013), even over large areas (Cuomo and Della Sala, 2013a). The triggering stage of both phenomena is related to ground infiltration, runoff and overland flow (Cuomo and Della Sala, 2013), which are key processes to be investigated. In addition, the mobilization of solid particles deserves a proper physical-based modeling whether a quantitative estimation of solid particles discharge at the outlet of mountain basin is required. In this work, the approaches for soil superficial erosion analysis are firstly reviewed; then, a relevant case study of two medium-sized mountain basins, affected by flow-like phenomena with huge consequences (Cascini et al., 2009) is presented, which motivates a parametric numerical analysis with a physically-based model carried out for a wide class of soil properties and rainfall scenarios (Cuomo et al., 2013b). The achieved results outline that the peak discharge of water and solid particles driven by overland flow depends on rainfall intensity while volumetric solid concentration within the washout is related to the morphometric features of the whole mountain basin. Furthermore, soil suction is outlined as a key factor for the spatial-temporal evolution of infiltration and runoff in the basin, also affecting the discharge of water and solid particles at the outlet of the basin. Based on these insights, selected cases are analyzed aimed to provide a wide class of possible slope erosion scenarios. It is shown that, provided the same amount of cumulated rainfall, the sequence of high and low intensity rainfall events strongly affects the time-discharge at the outlet of the basin without significant variations of the maximum volumetric solid concentration. References Cascini, L., Cuomo, S., Ferlisi, S., Sorbino, G. (2009). Detection of mechanisms for destructive landslides in Campania region-southern Italy. Proc. of the first Italian Workshop on Landslides, 8-10 June 2009 Naples, Italy, vol 1. Studio Editoriale Doppiavoce, Naples, pp 43-51. Cascini, L., Sorbino, G., Cuomo, S., Ferlisi, S. (2013). Seasonal effects of rainfall on the shallow pyroclastic deposits of the Campania region (southern Italy). Landslides, 1-14, DOI: 10.1007/s10346-013-0395-3. Cuomo S., Della Sala M. (2013a). Spatially distributed analysis of shallow landslides and soil erosion induced by rainfall. (submitted to Natural Hazards). Cuomo, S., Della Sala, M. (2013b). Rainfall-induced infiltration, runoff and failure in steep unsaturated shallow soil deposits. Engineering Geology. 162, 118-127. Cuomo, S., Della Sala, M., Novità A. (2013). Physically-based modeling of soil erosion induced by rainfall on steep slopes. (submitted to Geomorphology).

Similarities in chemical composition of soil organic matter across a millennia-old paddy soil chronosequence as revealed by advanced solid-state NMR spectroscopy

USDA-ARS?s Scientific Manuscript database

Soil organic matter (SOM) accumulation in paddy soils has aroused considerable attention due to its vital significance in global food, energy, climate, and environmental issues. Considerable progress has been made toward the understanding of changes in the quantity of SOM in paddy soils over a mille...

Effects of buried obstacles on penetration resistance in cohesionless soils

NASA Technical Reports Server (NTRS)

Deluca, E. W.; Carrasco, L. H.

1972-01-01

Recent experiments concerning penetration of cohesionless soils in special molds that include solid obstacles embedded within the soil matrix are reported. The relative effects of these obstacles with respect to the soil properties of relative density, texture, and gradation are also discussed. Because lunar soil is fairly cohesionless, special attention was given to the Apollo lunar simulant, AP-12.

Influence of environmental changes on the biogeochemistry of arsenic in a soil polluted by the destruction of chemical weapons: A mesocosm study.

PubMed

Thouin, Hugues; Battaglia-Brunet, Fabienne; Norini, Marie-Paule; Le Forestier, Lydie; Charron, Mickael; Dupraz, Sébastien; Gautret, Pascale

2018-06-15

Thermal destruction of chemical munitions from World War I led to the formation of a heavily contaminated residue that contains an unexpected mineral association in which a microbial As transformation has been observed. A mesocosm study was conducted to assess the impact of water saturation episodes and input of bioavailable organic matter (OM) on pollutant behavior in relation to biogeochemical parameters. Over a period of about eight (8) months, the contaminated soil was subjected to cycles of dry and wet periods corresponding to water table level variations. After the first four (4) months, fragmented litter from the nearby forest was placed on top of the soil. The mesocosm solid phase was sampled by three rounds of coring: at the beginning of the experiment, after four (4) months (before the addition of OM), and at the end of the experiment. Scanning electron microscopy coupled to energy dispersive X-ray spectroscopy observations showed that an amorphous phase, which was the primary carrier of As, Zn, and Cu, was unstable under water-saturated conditions and released a portion of the contaminants in solution. Precipitation of a lead arsenate chloride mineral, mimetite, in soils within the water saturated level caused the immobilization of As and Pb. Mimetite is a durable trap because of its large stability domain; however, this precipitation was limited by a low Pb concentration inducing that high amounts of As remained in solution. The addition of forest litter modified the quantities and qualities of soil OM. Microbial As transformation was affected by the addition of OM, which increased the concentration of both As(III)-oxidizing and As(V)-reducing microorganisms. The addition of OM negatively impacted the As(III) oxidizing rate, however As(III) oxidation was still the dominant reaction in accordance with the formation of arsenate-bearing minerals. Copyright © 2018 Elsevier B.V. All rights reserved.

Physico-chemo-mechanical coupling mechanisms in soil behavior

NASA Astrophysics Data System (ADS)

Hu, Liangbo

Many processes in geomechanics or geotechnical/geomechanical system engineering involve phenomena that are physical and/or chemical in nature, the understanding of which is crucial to modeling the mechanical responses of soils to various loads. Such physico-chemo-mechanical coupling mechanisms are prevalent in two different types of geomechanical processes studied in this dissertation: long-term soil/sediments compaction & desiccation cracking. Most commonly the underlying physical and chemical phenomena are explained, formulated and quantified at microscopic level. In addition to the necessity of capturing the coupling mechanisms, another common thread that emerges in formulating their respective mathematical model is the necessity of linking phenomena occurring at different scales with a theory to be formulated at a macroscopic continuum level. Part I of this dissertation is focused on the subject of long-term compaction behavior of soils and sediments. The interest in this subject arises from the need to evaluate reservoir compaction and land subsidence that may result from oil/gas extraction in petroleum engineering. First, a damage-enhanced reactive chemo-plasticity model is developed to simulate creep of saturated geomaterials, a long-term strain developed at constant stress. Both open and closed systems are studied. The deformation at a constant load in a closed system exhibits most of the characteristics of the classical creep. Primary, secondary and tertiary creep can be interpreted in terms of dominant mechanisms in each phase, emphasizing the role of the rates of dissolution and precipitation, variable reaction areas and chemical softening intensity. The rest of Part I is devoted to the study of soil aging, an effect of a localized mineral dissolution related creep strain and subsequent material stiffening. A three-scale mathematical model is developed to numerically simulate the scenarios proposed based on macroscopic experiments and geochemical evidence. These scale are: micro-scale for intra-grain dissolution, meso-scale for processes within grain assembly and macro-scale of a granular continuum. This model makes it possible to predict the porosity evolution starting from a very simple grain assembly under different pressures at the rneso-scale and evaluate the evolution of the stiffness as a function of the aging duration and the associated stress at the macro-scale. The results are qualitative but reproduce well the main phenomena and tendencies. Subsequently, this model is further examined to study the feedback mechanisms in multi-scale phenomena of sediment compaction and their role in chemo-hydro-geomechanical modeling. Part II of this dissertation deals with desiccation cracking of soils. Presence of cracks is a major cause for the deteriorated and compromised engineering properties of soils in earth works, such as dramatical increase in permeability or decrease of strength. Desiccation cracking is first addressed in an experimental study of shrinkage and cracking of a soil slab with water removed by isothermal drying. This study is followed by a numerical simulation of a solid phase continuum based on hygro-elastic theory. The experiments confirm that a substantial part of shrinkage occurs in the saturated phase and the kinematic boundary constraints play the crucial role in generating tensile stress and eventually cracks. Subsequently a novel experimental parametric study is performed using different liquids for the pore fluids in our experiment to further investigate the role of solid-fluid-gas interaction. Biot's theory is employed to perform a numerical parametric study. The amount of shrinkage depends mainly on the soil compressibility, on the other hand, the rate of fluid removal and rate of shrinkage are found to be controlled by evaporative and permeability properties. Additionally, microscopic experimental and phenomenological study is also performed to link the engineering properties and macroscopic variables to the phenomena occurring at the pore scale. Mercury Intrusion Porosimetry (MIP) technique is used to reveal the evolution of the pore sizes. The large pores are found to be mainly responsible for the shrinking deformation. A microscopic model is developed to simulate the possible scenarios during the entire desaturated phase. A possible quantitative comparison with MIP results and macroscopic experiments is made with using the averaging method to upscale the variables obtained at the micro-scale. The main characteristics of shrinkage behavior observed in macroscopic experiments are generally reproduced.

Filling the gap in Ca input-output budgets in base-poor forest ecosystems: The contribution of non-crystalline phases evidenced by stable isotopic dilution

NASA Astrophysics Data System (ADS)

van der Heijden, Gregory; Legout, Arnaud; Mareschal, Louis; Ranger, Jacques; Dambrine, Etienne

2017-07-01

In terrestrial ecosystems, plant-available pools of magnesium and calcium are assumed to be stored in the soil as exchangeable cations adsorbed on the surface of mineral and/or organic particles. The pools of exchangeable magnesium and calcium are measured by ion-exchange soil extractions. These pools are sustained in the long term by the weathering of primary minerals in the soil and atmospheric inputs. This conceptual model is the base of input-output budgets from which soil acidification and the sustainability of soil chemical fertility is inferred. However, this model has been questioned by data from long-term forest ecosystem monitoring sites, particularly for calcium. Quantifying the contribution of atmospheric inputs, ion exchange and weathering of both primary, secondary and non-crystalline phases to tree nutrition in the short term is challenging. In this study, we developed and applied a novel isotopic dilution technique using the stable isotopes of magnesium and calcium to study the contribution of the different soil phases to soil solution chemistry in a very acidic soil. The labile pools of Mg and Ca in the soil (pools in equilibrium with the soil solution) were isotopically labeled by spraying a solution enriched in 26Mg and 44Ca on the soil. Labeled soil columns were then percolated with a dilute acid solution during a 3-month period and the isotopic dilution of the tracers was monitored in the leaching solution, in the exchangeable (2 sequential 1 mol L-1 ammonium acetate extractions) and non-crystalline (2 sequential soil digestions: oxalic acid followed by nitric acid) phases. Significant amounts of Mg and Ca isotope tracer were recovered in the non-crystalline soil phases. These phases represented from 5% to 25% and from 24% to 50%, respectively, of the Mg and Ca labile pools during the experiment. Our results show that non-crystalline phases act as both a source and a sink of calcium and magnesium in the soil, and contribute directly to soil solution chemistry on very short-term time scales. These phases are very abundant in acid soils and, in the present study, represent a substantial calcium pool (equivalent in size to the Ca exchangeable pool). The gradual isotopic dilution of Mg and Ca isotope ratios in the leaching solution during the experiment evidenced an input flux of Mg and Ca originating from a pool other than the labile pool. While the Mg input flux originated primarily from the weathering of primary minerals and secondarily from the non-crystalline phases, the Ca input flux originated primarily from the non-crystalline phases. Our results also show that the net calcium release flux from these phases may represent a significant source of calcium in forest ecosystems and actively contribute to compensating the depletion of Ca exchangeable pools in the soil. Non-crystalline phases therefore should be taken into account when computing input-output nutrient budgets and soil acid neutralizing capacity.

Precipitation in Al–Mg solid solution prepared by solidification under high pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jie, J.C., E-mail: jiejc@dlut.edu.cn; School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001; Wang, H.W.

2014-01-15

The precipitation in Al–Mg solid solution containing 21.6 at.% Mg prepared by solidification under 2 GPa was investigated. The results show that the γ-Al{sub 12}Mg{sub 17} phase is formed and the β′ phase cannot be observed in the solid solution during ageing process. The precipitation of γ and β phases takes place in a non-uniform manner during heating process, i.e. the γ and β phases are first formed in the interdendritic region, which is caused by the inhomogeneous distribution of Mg atoms in the solid solution solidified under high pressure. Peak splitting of X-ray diffraction patterns of Al(Mg) solid solutionmore » appears, and then disappears when the samples are aged at 423 K for different times, due to the non-uniform precipitation in Al–Mg solid solution. The direct transformation from the γ to β phase is observed after ageing at 423 K for 24 h. It is considered that the β phase is formed through a peritectoid reaction of α + γ → β which needs the diffusion of Mg atoms across the interface of α/γ phases. - Highlights: • The γ phase is formed and the β′ phase is be observed in Al(Mg) solid solution. • Peak splitting of XRD pattern of Al(Mg) solid solution appears during aged at 150 °C. • The β phase is formed through a peritectoid reaction of α + γ → β.« less

The influence of vertical sorbed phase transport on the fate of organic chemicals in surface soils.

PubMed

McLachlan, Michael S; Czub, Gertje; Wania, Frank

2002-11-15

Gaseous exchange between surface soil and the atmosphere is an important process in the environmental fate of many chemicals. It was hypothesized that this process is influenced by vertical transport of chemicals sorbed to soil particles. Vertical sorbed phase transport in surface soils occurs by many processes such as bioturbation, cryoturbation, and erosion into cracks formed by soil drying. The solution of the advection/diffusion equation proposed by Jury et al. to describe organic chemical fate in a uniformly contaminated surface soil was modified to include vertical sorbed phase transport This process was modeled using a sorbed phase diffusion coefficient, the value of which was derived from soil carbon mass balances in the literature. The effective diffusivity of the chemical in a typical soil was greater in the modified model than in the model without sorbed phase transport for compounds with log K(OW) > 2 and log K(OA) > 6. Within this chemical partitioning space, the rate of volatilization from the surface soil was larger in the modified model than in the original model by up to a factor of 65. The volatilization rate was insensitive to the value of the sorbed phase diffusion coefficient throughout much of this chemical partitioning space, indicating that the surface soil layer was essentially well-mixed and that the mass transfer coefficient was determined by diffusion through the atmospheric boundary layer only. When this process was included in a non-steady-state regional multimedia chemical fate model running with a generic emissions scenario to air, the predicted soil concentrations increased by upto a factor of 25,whilethe air concentrations decreased by as much as a factor of approximately 3. Vertical sorbed phase transport in the soil thus has a major impact on predicted air and soil concentrations, the state of equilibrium, and the direction and magnitude of the chemical flux between air and soil. It is a key process influencing the environmental fate of persistent organic pollutants (POPs).

Evaluation of organic amendment on the effect of cadmium bioavailability in contaminated soils using the DGT technique and traditional methods.

PubMed

Yao, Yu; Sun, Qin; Wang, Chao; Wang, Pei-Fang; Ding, Shi-Ming

2017-03-01

Organic amendments have been widely proposed as a remediation technology for metal-contaminated soils, but there exist controversial results on their effectiveness. In this study, the effect of pig manure addition on cadmium (Cd) bioavailability in Cd-contaminated soils was systematically evaluated by one dynamic, in situ technique of diffusive gradients in thin films (DGT) and four traditional methods based on the equilibrium theory (soil solution concentration and the three commonly used extractants, i.e., acetic acid (HAc), ethylenediamine tetraacetic acid (EDTA), and calcium chloride (CaCl 2 ). Wheat and maize were selected for measurement of plant Cd uptake. The results showed that pig manure addition could promote the growth of two plants, accompanied by increasing biomasses of shoots and roots with increasing doses of pig manure addition. Correspondingly, increasing additions of pig manure reduced plant Cd uptake and accumulation, as indicated by the decreases of Cd concentrations in shoots and roots. The bioavailable concentrations of Cd in Cd-contaminated soils reflected by the DGT technique obviously decreased with increasing doses of pig manure addition, following the same changing trend as plant Cd uptake. Changes in soil solution Cd concentration and extractable Cd by HAc, EDTA, and CaCl 2 in soils were similar to DGT measurement. Meanwhile, the capability of Cd resupply from solid phase to soil solution decreased with increasing additions of pig manure, as reflected by the decreases in the ratio (R) value of C DGT to C sol . Positive correlations were observed between various bioavailable indicators of Cd in soils and Cd concentrations in the tissues of the two plants. These findings provide stronger evidence that pig manure amendment is effective in reducing Cd mobility and bioavailability in soils and it is an ideal organic material for remediation of Cd-contaminated soils.

Quantifying Water Infiltration through the Preferential Passages in the Forest Soil

NASA Astrophysics Data System (ADS)

Qu, Liqin; Chen, Ping; Gan, Ping; Lei, Tingwu

2017-04-01

Infiltration of water into soil commonly involves infiltration through the matrix body and preferential passages. Quantifying the contribution of preferential flow is important to evaluate the effects of land use and land cover changes on hillslope hydrology and watershed sedimentation. A new procedure was applied in this study to estimate the water infiltration into the soil through the soil body and macrospores. Field experiments were conducted in a forest field on the Loess Plateau at Tianshui Soil and Water Conservation Experimental Station, Gansu Province, China. The experiment implements a double-ring infiltrometer and involves two measuring phases. Firstly, a thin layer sieved soil collected on site was sprinkled on the nylon cloth to shelter the macrospores and to ensure that water infiltrates the soil through the matrix only. The infiltration process was measured, computed, and recorded. Secondly, immediately after the first phase, the nylon cloth and layered soil above the soil surface was removed from the double ring infiltrometer carefully, and the infiltration process was measured for 30 mins in which water infiltration through both soil body impacted by the preferential passages in the soil body. There were three treatments according to the measured infiltration periods in the first phase of 30, 60, 90 mins, respectively, and two replicates for each treatment were conducted. The measured soil infiltration curves in the first phase explained the transient process of soil matrix infiltration well. The measured date were fitted by Kostiako models fitted measured data well with all coefficients of determination greater than 0.9. The constant infiltration rates from the second phase were at least 2 times larger than the estimates from the first phase. In other words, the results indicated that more than 60% of water infiltration was through the preferential passages in the forest soil. The result also shows that durations in the first phase affect the trends of the infiltration curve in the second phase. The result from this study is helpful to understand the mechanism of hydrological response to different land covers.

Surface features of soil particles of three types of soils under different land use strategies

NASA Astrophysics Data System (ADS)

Matveeva, Nataliy; Kotelnikova, Anna; Rogova, Olga; Proskurnin, Mikhail

2017-04-01

Nowadays, there is a clear need in a deep investigation of molecular composition of soils and of its influence on surface characteristics of soil particles. The aim of this study is to evaluate the composition and properties of physical fractions in different soil types in determining functional specificity of soil solid-phase surface. The experiments were carried out with three different types of Russian soils—Sod-Podzolic, Chestnut, and Chernozem soils—under various treatments (fallow, different doses of mineral fertilizers and their aftereffects). The samples were separated into three fractions: silt (SF) with a particle size of <2 μm, light fraction (LF) with a density of <2 g/cm3, and residual fraction (RF) with a size >2 μm and the density >2 g/cm3. We measured specific surface area, surface hydrophobicity (contact angle, CA), ζ-potential, and the point of zero charge (PZC). For Chernozem and Chestnut soils and their fractions of we observed an increase in hydrophobicity for SF and RF under fertilizer treatment. At the sites not treated with fertilizers and aftereffect sites, the hydrophobicity of fractions was lower compared to the sites under treatment. The CA of the original soils and fractions were different: in 35% of cases CA was higher for SF and RF by 12-16%. The rest of samples demonstrated CA of all three physical fractions lower than CA of the original soil. The variability of the mean CA indicates considerable differences in ζ-potential and PZC between different types of soils and soil fractions. The results of potentiometric titration of PZC for Sod-Podzolic soil showed that all values are in acidic range, which suggests predominance of acidic functional groups at the surface of soil particles. Specific surface area determines soil sorption processes, bioavailability of nutrients, water etc. Here, specific surface area of Sod-Podzolic soil was low and SF-dependent. We calculated specific surface charge from obtained data on specific surface area and PZC. The results suggested considerable differences between sorption features of both soils and fractions under different land use strategies.

Scalability, Scintillation Readout and Charge Drift in a Kilogram Scale Solid Xenon Particle Detector

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoo, J.; Cease, H.; Jaskierny, W. F.

2014-10-23

We report a demonstration of the scalability of optically transparent xenon in the solid phase for use as a particle detector above a kilogram scale. We employ a liquid nitrogen cooled cryostat combined with a xenon purification and chiller system to measure the scintillation light output and electron drift speed from both the solid and liquid phases of xenon. Scintillation light output from sealed radioactive sources is measured by a set of high quantum efficiency photomultiplier tubes suitable for cryogenic applications. We observed a reduced amount of photons in solid phase compared to that in liquid phase. We used amore » conventional time projection chamber system to measure the electron drift time in a kilogram of solid xenon and observed faster electron drift speed in the solid phase xenon compared to that in the liquid phase.« less

Fuel spill identification using solid-phase extraction and solid-phase microextraction. 1. Aviation turbine fuels.

PubMed

Lavine, B K; Brzozowski, D M; Ritter, J; Moores, A J; Mayfield, H T

2001-12-01

The water-soluble fraction of aviation jet fuels is examined using solid-phase extraction and solid-phase microextraction. Gas chromatographic profiles of solid-phase extracts and solid-phase microextracts of the water-soluble fraction of kerosene- and nonkerosene-based jet fuels reveal that each jet fuel possesses a unique profile. Pattern recognition analysis reveals fingerprint patterns within the data characteristic of fuel type. By using a novel genetic algorithm (GA) that emulates human pattern recognition through machine learning, it is possible to identify features characteristic of the chromatographic profile of each fuel class. The pattern recognition GA identifies a set of features that optimize the separation of the fuel classes in a plot of the two largest principal components of the data. Because principal components maximize variance, the bulk of the information encoded by the selected features is primarily about the differences between the fuel classes.

Biochar Improves Performance of Plants for Mine Soil Revegetation

EPA Science Inventory

Biochar (the solid by-product of pyrolysis of biomass), has the potential to improve plant performance for revegetation of mine soils by improving soil chemistry, fertility, moisture holding capacity and by binding heavy metals. We investigated the effect of gasified conifer sof...

Solid-solid phase change thermal storage application to space-suit battery pack

NASA Astrophysics Data System (ADS)

Son, Chang H.; Morehouse, Jeffrey H.

1989-01-01

High cell temperatures are seen as the primary safety problem in the Li-BCX space battery. The exothermic heat from the chemical reactions could raise the temperature of the lithium electrode above the melting temperature. Also, high temperature causes the cell efficiency to decrease. Solid-solid phase-change materials were used as a thermal storage medium to lower this battery cell temperature by utilizing their phase-change (latent heat storage) characteristics. Solid-solid phase-change materials focused on in this study are neopentyl glycol and pentaglycerine. Because of their favorable phase-change characteristics, these materials appear appropriate for space-suit battery pack use. The results of testing various materials are reported as thermophysical property values, and the space-suit battery operating temperature is discussed in terms of these property results.

Leaching of PFC from soils contaminated with PFC of different origin

NASA Astrophysics Data System (ADS)

Kalbe, Ute; Piechotta, Christian; Rothe, Robert

2017-04-01

Leaching tests are fundamental tools for the assessment of groundwater impact by contaminated soils concerning the soil-groundwater pathway. Such procedures are supposed to serve as the basis for a reliable leachate prognosis. They can be applied to determine the short and long term leaching behaviour as well as the source term of contaminated soils. For this purpose two types of leaching procedures have been validated in Germany for the examination of the leaching behaviour of frequently occurring organic substances (DIN 19528 - column test and DIN 19529 - batch test). A liquid-to-solid ratio (L/S) of 2 L/kg and 10 L/kg) is the basis for the risk assessment which is implemented in different German regulations. The equivalence of test results for both tests for the same material under investigation has been investigated for a variety of pollutants in order to assess their reliability in compliance testing. However, for emerging pollutants there is hardly data available on this issue. Leaching tests on soils contaminated with emerging pollutants such as PFC (Perfluorinated Surfactants) are currently coming more into consideration due to the increasing detection of contaminated sites. Therefore, two soils were investigated in this study from different contamination source (paper sludge containing compost and fire distinguishing foam) using both leaching tests and both liquid-to-solid ratios. The leachability of the various perfluorinated compounds in relation to their content in solid matter was considered. Furthermore the eluate pre-treatment prior analysis (in particular liquid/solid separation step needed for batch tests) has been taken into account. The comparability of the results from batch and column is dependent on the solubility of the various compounds, on the L/S and on the turbidity in the eluates.

NMR Studies on the Aqueous Phase Photochemical Degradation of TNT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thorn, Kevin A.; Cox, Larry G.

2008-04-06

Aqueous phase photochemical degradation of 2,4,6-trinitrotoluene (TNT) is an important pathway in several environments, including washout lagoon soils, impact craters from partially detonated munitions that fill with rain or groundwater, and shallow marine environments containing unexploded munitions that have corroded. Knowledge of the degradation products is necessary for compliance issues on military firing ranges and formerly used defense sites. Previous laboratory studies have indicated that UV irradiation of aqueous TNT solutions results in a multicomponent product mixture, including polymerization compounds, that has been only partially resolved by mass spectrometric analyses. This study illustrates how a combination of solid and liquidmore » state 1H, 13C, and 15N NMR spectroscopy, including two dimensional analyses, provides complementary information on the total product mixture from aqueous photolysis of TNT, and the effect of reaction conditions. Among the degradation products detected were amine, amide, azoxy, azo, and carboxylic acid compounds.« less

A two-fluid model for avalanche and debris flows.

PubMed

Pitman, E Bruce; Le, Long

2005-07-15

Geophysical mass flows--debris flows, avalanches, landslides--can contain O(10(6)-10(10)) m(3) or more of material, often a mixture of soil and rocks with a significant quantity of interstitial fluid. These flows can be tens of meters in depth and hundreds of meters in length. The range of scales and the rheology of this mixture presents significant modelling and computational challenges. This paper describes a depth-averaged 'thin layer' model of geophysical mass flows containing a mixture of solid material and fluid. The model is derived from a 'two-phase' or 'two-fluid' system of equations commonly used in engineering research. Phenomenological modelling and depth averaging combine to yield a tractable set of equations, a hyperbolic system that describes the motion of the two constituent phases. If the fluid inertia is small, a reduced model system that is easier to solve may be derived.

15N-CPMAS nuclear magnetic resonace spectroscopy and biological stability of soil organic nitrogen in whole soil and particle-size fractions

Treesearch

R.J. DiCosty; D.P. Weliky; S.J. Anderson; E.A. Paul

2003-01-01

Soil organic nitrogen was quantified by solid-state 15N cross-polarization nuclear magnetic resonance spectroscopy (NMR) during a 14-month laboratory incubation of a sandy loam soil amended with 15N-clover. In whole soil and particle-size fractions, the clover-derived N was always 85-90% amide, 5 10% guanidinium N of...

Effect of pattern formation on C and N turnover heterogeneity in initial soils

NASA Astrophysics Data System (ADS)

Schaaf, Wolfgang; Zimmermann, Claudia

2013-04-01

The formation of vegetation patterns and hydrological processes, among others, result in soil heterogeneity in newly exposed land surfaces. We studied the effect of these developling structures on carbon and nitrogen trunover in soils of the artificial catchment Chicken Creek (Schaaf et al. 2011, 2012). Substrates with different physical and geochemical properties in combination with different labelled plant litter materials were studied in a microcosm experiment over a period of 80 weeks. Main objectives of the microcosm experiment were to determine the transformation processes of C and N from litter decomposition within the gaseous, liquid and solid phase, the interaction with mineral surfaces and its role for the establishment of biogeochemical cycles. The microcosm experiments were established in a climate chamber at constant 10 °C. In total, 48 soil columns (diameter: 14.4 cm; height: 30 cm) were filled with two different quaternary substrates (sand and loamy sand) representing the textural variation within the catchment at a bulk density of 1.4-1.5 g cm-3. The columns were automatically irrigated with artificial rainwater four times a day with 6.6 ml each (corresponding to 600 mm yr-1). The gaseous phase in the headspace of the microcosms was analyzed continuously for CO2 and N2O concentrations. C and N transformation processes were studied using 13C and 15N labelled litter of two different plant species occurring at the catchment (Lotus corniculatus, Calamagrostis epigejos) that was incorporated into the microcosm surface. By including litter from species with wide distribution within the catchment and soil substrates representing the main variation types of the sediments used for catchment construction we were able to characterize the general function of these sub-patches within the catchment with respect to litter decomposition, soil solution composition, DOC and nutrient leaching, and impact on the mineral soil phase. The results suggest that initial differences in substrate composition in combination with invading vegetation leads to the development of patterns with different biogeochemical process intensities within the catchment. These patterns are not mere additive effects of substrates plus litter, but reflect differences in element cycling. Schaaf, W., Bens, O., Fischer, A., Gerke, H.H., Gerwin, W., Grünewald, U., Holländer, H.M., Kögel-Knabner, I., Mutz, M., Schloter, M., Schulin, R., Veste, M., Winter, S. & Hüttl, R.F. (2011): Patterns and processes of initial terrestrial ecosystem development. J Plant Nutr Soil Sci, 174, 229-239. Schaaf, W., Elmer, M., Fischer, A., Gerwin, W., Nenov, R., Pretzsch, H., Seifert, S., Winter, S., Zaplata, M. (2012): Monitoring the formation of structures and patterns during initial development of an artificial catchment. Environmental Monitoring and Assessment. doi: 10.1007/s10661-012-2998-x.

Factors Controlling Carbon Metabolism and Humification in Different Soil Agroecosystems

PubMed Central

Doni, S.; Macci, C.; Peruzzi, E.; Ceccanti, B.; Masciandaro, G.

2014-01-01

The aim of this study was to describe the processes that control humic carbon sequestration in soil. Three experimental sites differing in terms of management system and climate were selected: (i) Abanilla-Spain, soil treated with municipal solid wastes in Mediterranean semiarid climate; (ii) Puch-Germany, soil under intensive tillage and conventional agriculture in continental climate; and (iii) Alberese-Italy, soil under organic and conventional agriculture in Mediterranean subarid climate. The chemical-structural and biochemical soil properties at the initial sampling time and one year later were evaluated. The soils under organic (Alberese, soil cultivated with Triticum durum Desf.) and nonintensive management practices (Puch, soil cultivated with Triticum aestivum L. and Avena sativa L.) showed higher enzymatically active humic carbon, total organic carbon, humification index (B/E3s), and metabolic potential (dehydrogenase activity/water soluble carbon) if compared with conventional agriculture and plough-based tillage, respectively. In Abanilla, the application of municipal solid wastes stimulated the specific β-glucosidase activity (extracellular β-glucosidase activity/extractable humic carbon) and promoted the increase of humic substances with respect to untreated soil. The evolution of the chemical and biochemical status of the soils along a climatic gradient suggested that the adoption of certain management practices could be very promising in increasing SOC sequestration potential. PMID:25614887

Electrical heating of soils using high efficiency electrode patterns and power phases

DOEpatents

Buettner, Harley M.

1999-01-01

Powerline-frequency electrical (joule) heating of soils using a high efficiency electrode configuration and power phase arrangement. The electrode configuration consists of several heating or current injection electrodes around the periphery of a volume of soil to be heated, all electrodes being connected to one phase of a multi-phase or a single-phase power system, and a return or extraction electrode or electrodes located inside the volume to be heated being connected to the remaining phases of the multi-phase power system or to the neutral side of the single-phase power source. This electrode configuration and power phase arrangement can be utilized anywhere where powerline frequency soil heating is applicable and thus has many potential uses including removal of volatile organic compounds such as gasoline and tricholorethylene (TCE) from contaminated areas.

Laboratory Jet Erosion Tests on the Lower American River Soil Samples, Sacramento, CA- Phase 2

DTIC Science & Technology

2017-05-01

ER D C/ G SL T R- 17 -8 Laboratory Jet Erosion Tests on the Lower American River Soil Samples, Sacramento, CA – Phase 2 G eo te ch ni...Jet Erosion Tests on the Lower American River Soil Samples, Sacramento, CA – Phase 2 Johannes L. Wibowo and Bryant A. Robbins Geotechnical and...Appendix B: Soil Mechanics Data ........................................................................................................... 71

Energy and Resource Saving of Steelmaking Process: Utilization of Innovative Multi-phase Flux During Dephosphorization Process

NASA Astrophysics Data System (ADS)

Matsuura, Hiroyuki; Hamano, Tasuku; Zhong, Ming; Gao, Xu; Yang, Xiao; Tsukihashi, Fumitaka

2014-09-01

An increase in the utilization efficiency of CaO, one of the major fluxing agents used in various steelmaking processes, is required to reduce the amount of discharged slag and energy consumption of the process. The authors have intensively focused on the development of innovative dephosphorization process by using so called "multi-phase flux" composed of solid and liquid phases. This article summarizes the research on the above topic done by the authors, in which the formation mechanisms of P2O5-containing phase during CaO or 2CaO·SiO2 dissolution into molten slag, the phase relationship between solid and liquid phases at equilibrium, and thermodynamic properties of P2O5-containing phase have been clarified. The reactions between solid CaO or 2CaO·SiO2 and molten CaO-FeO x -SiO2-P2O5 slag were observed by dipping solid specimen in the synthesized slag at 1573 K or 1673 K. The formation of the CaO-FeO layer and dual-phase layer of solid 2CaO·SiO2 and FeO x -rich liquid phase was observed around the interface from the solid CaO side toward the bulk slag phase side. Condensation of P2O5 into 2CaO·SiO2 phase as 2CaO·SiO2-3CaO·P2O5 solid solution was observed in both cases of CaO and 2CaO·SiO2 as solid specimens. Measurement of the phase relationship for the CaO-FeO x -SiO2-P2O5 system confirmed the condensation of P2O5 in solid phase at low oxygen partial pressure. The thermodynamics of 2CaO·SiO2-3CaO·P2O5 solid solution are to be clarified to quantitatively simulate the dephosphorization process, and the current results are also introduced. Based on the above results, the reduction of CaO consumption, the discharged slag curtailment, and energy-saving effects have been discussed.

Pyraclostrobin wash-off from sugarcane leaves and aerobic dissipation in agricultural soil.

PubMed

Fulcher, James M; Wayment, Darcey G; White, Paul M; Webber, Charles L

2014-03-12

To mitigate damage from the fungal sugarcane pathogen brown rust (Puccinia melanocephala), a Section 18 Emergency Use Label was put in place by the United States Environmental Protection Agency (U.S. EPA) for the application of pyraclostrobin (trade name Headline SC, produced by BASF, Research Triangle Park, NC) on sugarcane in 2008. To assess the dynamics of this fungicide in Louisiana soil, samples (n = 24) from a non-treated field were spiked with pyraclostrobin (3.1 μg g(-1)) and analyzed in laboratory conditions over the course of 63 days using quick, easy, cheap, effective, rugged, and safe (QuEChERS) dispersive solid-phase extraction/high-performance liquid chromatography with ultraviolet-visible detection (dSPE/HPLC-UV). Modeling was performed using Microsoft Excel to predict DTx values. Pyraclostrobin was found to follow biphasic kinetics with DT50 and DT90 values of 60 and 282 days, suggesting that it is moderately persistent to persistent in soils. Wash-off studies on sugarcane indicate that very little fungicide is in the wash-off after 48 h. If applied to sugarcane according to label recommendations, the fungicide should have minimal dissipation from rainfall events.