Biomedical subjects

Murray B McBride

Publications and source records attributed to Murray B McBride.

8 recordsLinked to original sources

PubMed2006

A test of sequential extractions for determining metal speciation in sewage sludge-amended soils.

Sequential extraction procedures are widely used to estimate the quantity of trace metals bound to different solid fractions in contaminated soils. However, reliability of speciation of trace metals by these procedures remains largely unexamined. In the present study, the selectivity of each extraction step was tested by observing the effect of reversing the extraction order in the procedure. Two different sequential extraction methods and their reversed modes were used for metal fractionation in sewage sludge-amended soils. Significantly increased amounts of extractable metals (Cd, Cu, Pb and Zn) were evident in the sludge-amended soils compared to control soil by all extraction schemes; however, the amounts of metals extracted by each step were strongly dependent on the order of extraction, the type of reagents and the nature of the individual metals. Caution is advised in deducing the forms of soil metals from sequential extraction results from metal-contaminated soils.

Cadmium↗

PubMed2005

Environmental factors determining the trace-level sorption of silver and thallium to soils.

Silver (Ag) and thallium (Tl) are nonessential elements that can be highly toxic to a number of biota even when present in the environment at trace levels. In spite of that, the literature on the chemistry and fate of Ag and Tl in soils is extremely scanty. In that context, the key objective of this research was to compare the sorption characteristics of trace amounts of Ag and Tl on a range of soils and minerals. A second objective was to determine the extent to which the composition and surface chemistry of the sorbents, as well as other environmental factors (simulated acid rain application and the presence of competing ions like K+ and NH4+) influence the sorption and lability of Ag and Tl. To this end, short-term and long-term sorption isotherms were generated under batch conditions for trace levels of Ag and Tl onto three illite-rich mineral soils from central New York (silt loam and fine sandy loam), a peaty-muck soil drained for agricultural use, and soil minerals (ferrihydrite and birnessite). Silver sorbed more strongly than thallium to all the soils. The peaty-muck soil sorbed Ag more strongly than the mineral soils, confirming that silver sorption to soils is dominated by soil organic matter either through exchange or complexation. The organic matter-rich soil's retention of Tl, however, was similar to that of the sandy soil. Amounts of Ag and Tl sorbed to the mineral soils increased after a 1-year incubation period. Whereas Ag sorption to the peaty-muck soil also increased with time, Tl sorption was unaffected. Short batch studies indicated that high amounts of Tl sorb to birnessite (30% by mass). However, subsequent X-ray diffraction (XRD) analysis of the solid did not detect the presence of any Tl3+ as Tl2O3 on the MnO4. In contrast, TlI was relatively poorly sorbed on noncrystalline ferrihydrite at pH 5.1 (1.5% by mass). Thus, Mn oxides may play a role in Tl retention by soils; whereas, contrary to previous reports, iron oxides do not effectively sorb Tl. Acid rain and addition of potassium (K+) and ammonium (NH4+) as competing ions had no long-term effect on Ag or Tl sorption. Thallium remaining in the all the batch sorption solutions, as determined by flame atomic absorption spectroscopy (FAAS) and differential pulse anodic stripping voltametry (DPASV), was completely labile, which may have important environmental consequences.

Adsorption↗

PubMed2005

Reduction of silver solubility by humic acid and thiol ligands during acanthite (beta-Ag2S) dissolution.

Precipitation of highly insoluble metal sulfide minerals like acanthite (beta-Ag2S) or red cinnabar (HgS) is in principle an effective means to reduce metal availability and toxicity in contaminated soils. Unfortunately, experiments have shown that red cinnabar may be solubilized in the presence of dissolved organic matter or thiol ligands. To determine whether the same applies to acanthite, a laboratory synthesized beta-Ag2S mineral was incubated for up to 3 weeks in the presence of KNO3, dissolved humic acids, cysteine, methionine and thiosulfate. XPS analysis identified Ag2O (52%), Ag2SO4 (8%) and Ag2S (40%) on the particle surfaces. Ag was released into solution in the presence of KNO3 and methionine, presumably from mixed-oxidation surface layers. Contrary to earlier results with cinnabar, however, humic acids reduced Ag concentrations in solution by about 75%, and cysteine and thiosulfate, each containing a free -SH functional group, almost completely suppressed Ag release into solution.

Humans↗

PubMed2004

Microbial acidification and pH effects on trace element release from sewage sludge.

Leaching of sludge-borne trace elements has been observed in experimental and field studies. The role of microbial processes in the mobilization of trace elements from wastewater sludge is poorly defined. Our objectives were to determine trace element mobilization from sludge subjected to treatments representing microbial acidification, direct chemical acidification and no acidification, and to determine the readsorption potential of mobilized elements using calcareous sand. Triplicate columns (10-cm diameter) for incubation and leaching of sludge had a top layer of digested dewatered sludge (either untreated, acidified with H2SO4, or limed with CaCO3; all mixed with glass beads to prevent ponding) and a lower glass bead support bed. Glass beads in the sludge layer, support layer or both were replaced by calcareous sand in four treatments used for testing the readsorption potential of mobilized elements. Eight sequential 8-day incubation and leaching cycles were operated, each consisting of 7.6 d of incubation at 28 degrees C followed by 8 h of leaching with synthetic acid rain applied at 0.25 cm/h. Leachates were analyzed for trace elements, nitrate and pH, and sludge layer microbial respiration was measured. The largest trace element, nitrate and S losses occurred in treatments with the greatest pH depression and greatest microbial respiration rates. Cumulative leaching losses from both microbial acidification and direct acidification treatments were > 90% of Zn and 64-80% of Cu and Ni. Preventing acidification with sludge layer lime or sand restricted leaching for all trace elements except Mo. Results suggested that the primary microbial role in the rapid leaching of trace elements was acidification, with results from direct acidification being nearly identical to microbial acidification. Microbial activity in the presence of materials that prevented acidification mobilized far lower concentrations of trace elements, with the exception of Mo. Trace elements mobilized by acidification were readsorbed by calcareous sand when present.

Calcium↗

PubMed2003

Effect of microbial activity on trace element release from sewage sludge.

The microbial role in mobilization of trace elements from land-applied wastewater sludge is not well-defined. Our study examined the leachability of trace elements (Cd, Cr, Cu, Mo, Ni, P, Pb, S, and Zn) from dewatered sludge as affected by treatments designed to alter microbial activity. Different levels of microbial activity were achieved by incubating sludge columns at 4, 16, 28, and 37 degrees C and by the addition of AgNO3 biocide at each temperature. Columns (with inert glass bead support beds) were subjected to six consecutive incubation-leaching cycles, each consisting of 7.3-d incubation followed by 16-h leaching with synthetic acid rain. Glucose mineralization tests were used to assess overall microbial activity. Significant acidification and trace element leaching occurred when conditions favored microbial activity (16 and 28 degrees C). Extent of mobilization was element-specific with Zn, Ni, and Cu showing the greatest mobilization (99, 67, and 57%, respectively). Mobilization was reduced but still substantial at 4 degrees C. Conditions that best inhibited microbial activity (37 degrees C or biocide at any temperature) resulted in the least mobilization. Characterization of enrichments performed using thiosulfate as the sole energy source revealed the presence of both known and putative S-oxidizing bacteria in the sludge. The results suggest that microbial acidification via S oxidation can mobilize trace elements from sludge. Elemental mobility in field situations would also be governed by other factors, including the capacity of soil to buffer acidification and to adsorb mobilized elements.

Adsorption↗

PubMed2003

Aging and temperature effects on DOC and elemental release from a metal contaminated soil.

The combined effect of time and temperature on elemental release and speciation from a metal contaminated soil (Master Old Site, MOS) was investigated. The soil was equilibrated at 10, 28, 45, 70 and 90 degrees C for 2 days, 2 weeks, and 2 months in the laboratory. Dissolved organic carbon (DOC), total soluble elements (by ICP), and labile metals (by DPASV) were determined in the filtered (0.22 microm) supernatants. For the samples equilibrated at 90 degrees C, DOC fractions were size fractionated by filtration and centrifugation; a subsample was only centrifuged while another was also filtered through a 0.45 microm filter. Analyses of the supernatants (ICP, DPASV, DOC) were performed on all size fraction subsamples. Dissolved organic carbon (DOC) increased both with temperature and incubation time; however, metal behavior was not as uniform. In general, total soluble metal release (ICP) paralleled the behavior of DOC, increasing with both time and temperature, and confirming the importance of soil organic matter (SOM) in metal retention. Voltammetric analysis (dpasv) of Cu and Zn showed that very little of these metals remains labile in solution due, presumably, to complexation with dissolved organic matter. Labile concentrations of Cd, on the other hand, constituted a significant portion (50%) of total soluble Cd. Copper and Al increased in solution with time (up to 2 months) and temperature up to 70 degrees C; however, at 90 degrees C the soluble concentration declined sharply. The same behavior was observed after equilibration for longer periods of time (550 days) at lower temperatures (23 and 70 degrees C). While concentrations of labile Cu and total soluble Cu and Al increased in the unfiltered samples, the trend remained the same. DPASV analysis showing shifts in labile Cu complexes with temperature and time, together with the results from the unfiltered samples, lead to the hypothesis that Cu was complexing with large polymers that could form at the elevated temperature, and thus be removed from the analyzed solution. It is possible that Cu and Al released by SOM oxidation has re-sorbed or complexed to more recalcitrant organic matter or to mineral phases. Variations in the relative molecular size fractions present within the DOC pool produced by increased time and temperature may influence the element-DOC complexes present in solution and their behavior in soil environments.

Metals, Heavy↗

PubMed2002

Zinc-sulfur and cadmium-sulfur association in metalliferous peats: evidence from spectroscopy, distribution coefficients, and phytoavailability.

Peat deposits can concentrate chalcophilic metals such as Zn and Cd by biogeochemical processes; as a result, there is a possibility that the solubility, mobility, and bioavailability of these metals could increase when such deposits are drained and cropped, initiating oxidation of organic matter and sulfides under aerobic conditions. We use spectroscopic, chemical, and bioassay approaches to characterize high Zn (88-15,800 mg kg(-1)), Cd (0.55-83.0 mg kg(-1)), and S (3.52-9.54 g kg(-1)) peat soils collected from locations in New York State and Ontario that overlie Silurian-age metal-enriched dolomite bedrock. Total and KNO3-extractable trace metals were determined by ICP emission spectrometry, and labile Cd and Zn were measured in the KNO3 extracts by anodic stripping voltammetry. A greenhouse bioassay with maize and canola was conducted to determine the bioavailability and toxicity of the soil Zn and Cd. The electronic oxidation states of sulfur in the peat soils were determined by X-ray absorption near edge spectroscopy (XANES) and Zn and S distribution in soil particles by energy-dispersive X-ray absorption (EDX) spectroscopy. Sulfur-XANES analyses show that a high percentage (35-45%) of the total soil S exists in the most reduced electronic oxidation states (such as sulfides and thiols), while <5% exists in the most oxidized forms (such as sulfate). EDX analyses indicate a microscopic elemental association between Zn and S in these soils. Despite the EDX evidence of close association between Zn and S in soil particles, conventional X-ray diffraction analyses of the bulk soils did not detect a mineral phase of sphalerite (ZnS) in any of the soils. The distribution coefficients (Kd) for Zn and Cd increased with soil pH and indicated stronger Cd retention than Zn in the peats. The results of the bioassaytests showed that most of the high-Zn soils were very phytotoxic, with plant shoot Zn levels exceeding 400 mg kg(-1). Conversely, Cd concentrations in the plant shoots were generally below 2 mg kg(-1), showing a tendency toward low Cd phytoavailability relative to Zn. The information gained from the spectroscopic analyses (S-XANES and EDX) was used to explain the macroscopic observations (Cd and Zn Kd values and phytoavailability data) in these peat soils; we conclude that sulfur biogeochemical cycling may play an important role in Zn and Cd retention in these organic soils.

Biological Availability↗

PubMedDate not supplied

Temperature and microbial activity effects on trace element leaching from metalliferous peats.

Due to geochemical processes, peat soils often have elevated concentrations of trace elements, which are gradually released following drainage for agriculture. Our objectives were to use incubation temperatures to vary microbial activity in two metalliferous peats (M7 acidic peat and M3 neutral peat) from the Elba, New York region, and to use periodic leaching to assess the extent of trace element release from these soils. Dried soils were mixed with glass beads to maintain aeration, moistened, and incubated at 4, 16, 28, and 37 degrees C in 10-cm-diameter x 8-cm-tall columns. Five incubation-leaching cycles were performed, each consisting of 7.3 d of incubation (28 d for the final cycle) followed by 16 h of leaching with synthetic acid rain at 2.5 mm h(-1). Microbial activity was determined initially and after the final leaching by measuring C mineralization following glucose stimulation. Cumulative respiration results were ranked 28 > 16 > 4 > 37 degrees C, with M7 acidic peat respiration values greater than M3 neutral peat at each temperature. Initial leachate pH levels were between 2 and 4, with acidification less pronounced and shorter-lived for the M3 peat. Leachate S, dissolved organic carbon (DOC), NO3-N, and trace elements declined with successive leachings (rebounding slightly in the final M3 leachate), with concentrations typically greater in the M7 leachate. Elemental losses followed the same general ranking (28 > 16 > 4 > 37 degrees C); losses at 28 degrees C were 15 to 22% for As, Cd, Ni, and Zn from the M7 peat; losses from M3 were comparable only for Cu (1%) and Ni (19%). The correlation of respiration with S, DOC, and trace elements losses indicates that microbial processes mediated the release of trace elements in both peat soils. Neutral M3 peat pH levels limited losses of most analytes.

Agriculture↗