RESUMEN
Long-term speciation and lability of silver (Ag-), silver chloride (AgCl-), and silver sulfide nanoparticles (Ag2S-NPs) in soil were studied by X-ray absorption spectroscopy (XAS), and newly developed "nano" Diffusive Gradients in Thin Films (DGT) devices. These nano-DGT devices were designed specifically to avoid confounding effects when measuring element lability in the presence of nanoparticles. The aging profile and stabilities of the three nanoparticles and AgNO3 (ionic Ag) in soil were examined at three different soil pH values over a period of up to 7 months. Transformation of ionic Ag, Ag-NP and AgCl-NPs were dependent on pH. AgCl formation and persistence was observed under acidic conditions, whereas sulfur-bound forms of Ag dominated in neutral to alkaline soils. Ag2S-NPs were found to be very stable under all conditions tested and remained sulfur bound after 7 months of incubation. Ag lability was characteristically low in soils containing Ag2S-NPs. Other forms of Ag were linked to higher DGT-determined lability, and this varied as a function of aging and related speciation changes as determined by XAS. These results clearly indicate that Ag2S-NPs, which are the most environmentally relevant form of Ag that enter soils, are chemically stable and have profoundly low Ag lability over extended periods. This may minimize the long-term risks of Ag toxicity in the soil environment.
Asunto(s)
Monitoreo del Ambiente/métodos , Nanopartículas del Metal/química , Compuestos de Plata/análisis , Plata/análisis , Contaminantes del Suelo/análisis , Difusión , Concentración de Iones de Hidrógeno , Iones , Suelo/química , Espectroscopía de Absorción de Rayos XRESUMEN
In cities nationwide, urban agriculture has been put on hold because of the high costs of soil testing for historical contaminants such as lead (Pb). The Mehlich-3 soil test is commonly used to determine plant available nutrients, is inexpensive, and has the potential to estimate trace metals in urban soil. The objectives of this study are to evaluate the ability of the Mehlich-3 to estimate total Pb and bioaccessible Pb in vacant residential lots. Total and bioaccessible Pb were determined in 68 vacant residential lots in Cleveland, OH, using standard USEPA Method 3051A and the Relative Bioaccessibility Leaching Procedure (RBALP), respectively. The Mehlich-3 soil test was used to determine extractable Pb, and the results show Mehlich-3 was strongly correlated with total and bioaccessible Pb. The Mehlich-3 soil test could be used as a screening tool to not only estimate total Pb (slope 1.73, = 0.970) but also to estimate bioaccessible Pb when using RBALP at pH 1.5 (slope 1.67, = 0.975) and RBALP at pH 2.5 (slope 1.15, = 0.938). Additional samples were collected from the Thackeray Avenue site in Cleveland, OH, to demonstrate the ability of the Mehlich-3 soil test to screen soil for Pb. The results from the Thackeray site show good agreement between Mehlich-3 and the standard USEPA methods. A screening protocol for urban vacant residential lots using the Mehlich-3 soil test is proposed.
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Contaminantes del Suelo , Suelo , Ciudades , Plomo , PlantasRESUMEN
In the western United States, sugar beet processing for sugar recovery generates a lime-based waste product (â¼250,000 Mg yr) that has little liming value in the region's calcareous soils. This area has recently experienced an increase in dairy production, with dairies using copper (Cu)-based hoof baths to prevent hoof diseases. A concern exists regarding soil Cu accumulation because spent hoof baths may be disposed of in waste ponds, with pond waters being used for irrigation. The objective of this preliminary study was to evaluate the ability of lime waste to sorb Cu. Lime waste was mixed with increasing Cu-containing solutions (up to 100,000 mg Cu kg lime waste) at various buffered pH values (pH 6, 7, 8, and 9) and shaken over various time periods (up to 30 d). Copper sorption phenomenon was quantified using sorption maximum fitting, and the sorption mechanism was investigated using X-ray absorption spectroscopy. Results showed that sorption onto lime waste increased with decreasing pH and that the maximum Cu sorption of â¼45,000 mg kg occurred at pH 6. X-ray absorption spectroscopy indicated that Cu(OH) was the probable species present, although the precipitate existed as small multinuclear precipitates on the surface of the lime waste. Such structures may be precursors for larger surface precipitates that develop over longer incubation times. Findings suggest that sugar beet processing lime waste can viably sorb Cu from liquid waste streams, and thus it may have the ability to remove Cu from spent hoof baths.
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Beta vulgaris , Cobre , Adsorción , Carbohidratos , Cobre/química , Concentración de Iones de Hidrógeno , Suelo , Espectroscopía de Absorción de Rayos XRESUMEN
Excessive Cu concentrations in water systems can negatively affect biological systems. Because Cu can form strong associations with organic functional groups, we examined the ability of biochar (an O-C-enriched organic bioenergy by-product) to sorb Cu from solution. In a batch experiment, KOH steam-activated pecan shell biochar was shaken for 24 h in pH 6, 7, 8, or 9 buffered solutions containing various Cu concentrations to identify the effect of pH on biochar Cu sorption. Afterward, all biochar solids from the 24-h shaking period were air-dried and analyzed using X-ray absorption fine structure (XAFS) spectroscopy to determine solid-phase Cu speciation. In a separate batch experiment, biochar was shaken for 30 d in pH 6 buffered solution containing increasing Cu concentrations; the Cu sorption maximum was calculated based on the exponential rise to a maximum equation. Biochar sorbed increasing amounts of Cu as the solution pH decreased from 9 to 6. The XAFS spectroscopy revealed that Cu was predominantly sorbed onto a biochar organic phase at pH 6 in a molecular structure similar to Cu adsorbed on model humic acid (Cu-humic acid [HA]). The XAFS spectra at pH 7, 8, and 9 suggested that Cu was associated with the biochar as three phases: (i) a complex adsorbed on organic ligands similar to Cu-HA, (ii) carbonate phases similar to azurite (Cu(CO)(OH)), and (iii) a Cu oxide phase like tenorite (CuO). The exponential rise equation fit to the incubated samples predicted a Cu sorption maximum of 42,300 mg Cu kg. The results showed that KOH steam-activated pecan shell biochar could be used as a material for sorbing excess Cu from water systems, potentially reducing the negative effects of Cu in the environment.
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Carbón Orgánico/química , Cobre/química , Vapor , Adsorción , Animales , Carya , Bovinos , Industria Lechera , Concentración de Iones de Hidrógeno , Hidróxidos , Compuestos de Potasio , Semillas , Espectroscopía de Absorción de Rayos XRESUMEN
Arsenic (As) contamination of rice grains and the generally low concentration of micronutrients in rice have been recognized as a major concern for human health. Here, we investigated the speciation and localization of As and the distribution of (micro)nutrients in rice grains because these are key factors controlling bioavailability of nutrients and contaminants. Bulk total and speciation analyses using high-pressure liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) and X-ray absorption near-edge spectroscopy (XANES) was complemented by spatially resolved microspectroscopic techniques (micro-XANES, micro-X-ray fluorescence (micro-XRF) and particle induced X-ray emission (PIXE)) to investigate both speciation and distribution of As and localization of nutrients in situ. The distribution of As and micronutrients varied between the various parts of the grains (husk, bran and endosperm) and was characterized by element-specific distribution patterns. The speciation of As in bran and endosperm was dominated by As(III)-thiol complexes. The results indicate that the translocation from the maternal to filial tissues may be a bottleneck for As accumulation in the grain. Strong similarities between the distribution of iron (Fe), manganese (Mn) and phosphorus (P) and between zinc (Zn) and sulphur (S) may be indicative of complexation mechanisms in rice grains.
Asunto(s)
Arsénico/metabolismo , Minerales/metabolismo , Oryza/metabolismo , Semillas/metabolismo , Transporte Biológico , Cromatografía Líquida de Alta Presión , Fluorescencia , Polvos , Estándares de Referencia , Espectrofotometría Atómica , Análisis Espectral , Rayos XRESUMEN
Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.
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Metales/metabolismo , Análisis Espectral/métodos , Fluorescencia , Rayos XRESUMEN
Zero-valent iron nanoparticles (nZVI) have been widely tested as they are showing significant promise for environmental remediation. However, many recent studies have demonstrated that their mobility and reactivity in subsurface environments are significantly affected by their tendency to aggregate. Both the mobility and reactivity of nZVI mainly depends on properties such as particle size, surface chemistry and bulk composition. In order to ensure efficient remediation, it is crucial to accurately assess and understand the implications of these properties before deploying these materials into contaminated environments. Many analytical techniques are now available to determine these parameters and this paper provides a critical review of their usefulness and limitations for nZVI characterisation. These analytical techniques include microscopy and light scattering techniques for the determination of particle size, size distribution and aggregation state, and X-ray techniques for the characterisation of surface chemistry and bulk composition. Example characterisation data derived from commercial nZVI materials is used to further illustrate method strengths and limitations. Finally, some important challenges with respect to the characterisation of nZVI in groundwater samples are discussed.
RESUMEN
The inability to determine metal species in soils hampers efforts to understand the mobility, bioavailability, and fate of contaminant metals in environmental systems, to assess health risks posed by them, and to develop methods to remediate metal contaminated sites. Fortunately, great strides have been made in the development of methods of species characterization and in their application to the analysis of particulates and mixtures of solid phases in physics, analytical chemistry, and materials science. This manuscript highlights a selection of the analytical methods available today offering the greatest promise, briefly describes the fundamental processes involved, examines their limitations, points to how they have been used in the environmental and geochemical literature, and offers some suggested research directions in the hope of stimulating further investigation into the application of these powerful tools to the problems outlined above.
Asunto(s)
Técnicas de Química Analítica/instrumentación , Técnicas de Química Analítica/métodos , Metales Pesados/química , Suelo/análisisRESUMEN
The use of biosolids in agriculture continues to be debated, largely in relation to their metal contents. Our knowledge regarding the speciation and bioavailability of biosolids metals is still far from complete. In this study, a multi-technique approach was used to investigate copper and zinc speciation and partitioning in one contemporary and two historical biosolids used extensively in previous research and field trials. Using wet chemistry and synchrotron spectroscopy techniques it was shown that copper/zinc speciation in the biosolids was largely equivalent despite the biosolids being derived from different countries over a 50 year period. Furthermore, copper speciation was consistently dominated by sorption to organic matter whereas Zn partitioned mainly to iron oxides. These data suggest that the results of historical field trials are still relevant for modern biosolids and that further risk assessment studies should concentrate particularly on Cu as this metal is associated with the mineralisable biosolids fraction.