Influence of x-ray diffraction sample preparation on quantitative mineralogy: implications for chromate waste treatment

Powders of chromite ore processing residue (COPR) were mineralogically evaluated using quantitative X-ray powder diffraction (XRPD) to illustrate the impacts of sample preparation procedures. Chromite ore processing residue is strongly alkaline, reactive, contains minerals of varying hardness and absorption coefficients, and exhibits significant amorphicity. This poses a challenge to produce powders for XRPD analysis that are sufficiently fine and of uniform particle size while avoiding mineral reactions and overgrinding effects. Dry, hand pulverization to different grain sizes, and wet, mechanical pulverization (micromilling) using four milling liquids (cyclohexane, isopropanol, ethanol, and water), and variable milling durations (up to 15 min) were evaluated. Micromilling with a light, nonpolar, highly evaporative liquid such as cyclohexane with a milling time of 5 min mitigated systematic errors such as microabsorption and preferred orientation as it produced finer and more uniform particle size distributions than the hand-pulverized powders, while simultaneously affording the least time for sample preparation. Conversely, the use of water as milling liquid resulted in extensive hydration reactions during sample preparation, causing mischaracterization and significant underestimation of its reactive brownmillerite content, which can complicate the remediation design process for COPR. Hand pulverization emerged as a necessary complement to quantify Cr(VI)-containing, softer minerals destroyed during mechanical milling, the quantification of which has also important implications for COPR treatment design. The findings of this study may be applicable in a variety of geochemically complicated and reactive environmental media (metal-contaminated soils, stabilized/solidified media, inorganic waste), and points to the importance of the sample preparation method to obtain reliable quantitative XRPD results.     

Assessment of environmental endocrine disruptors in bald eagles of the Great Lakes

Environmental endocrine disruption in wildlife has primarily focused on estrogenic/androgenic end points and their antagonists. We describe here the work that has occurred within the Great Lakes of North America that has used the bald eagle (Haliaeetus leucocephalus) as a sentinel species of the effects of environmental toxicants, including endocrine disruption. Our data suggests that population level effects of hormone disrupting chemicals, not necessarily estrogen/androgen mimics and their antagonists, have been associated with reproductive and teratogenic effects observed in the bald eagle population within the Great Lakes Basin. Additional laboratory and field studies are necessary to further clarify the role of environmental endocrine disruptors on reproduction in avian populations. The use of sea eagles (Haliaeetus spp.) as biosentinels of pollution in other regions of the world is also discussed.     

Swelling related to ettringite crystal formation in chromite ore processing residue

Several million tons of Chromite Ore Processing Residue (COPR) were deposited at two sites in New Jersey and Maryland, USA, and over time they exhibited extensive heaving phenomena. Ettringite, a needle-shaped mineral and an expansive mineral commonly recognized in the literature concerning cement- and soil, has been identified extensively in numerous COPR samples collected from these sites. It was therefore believed that ettringite formation and its crystal growth are strongly associated with COPR heaving. We investigated the correlation between ettringite and the heaving phenomena in COPR materials that contained no initial ettringite. Two identical COPR samples were exposed to a 4% w/w sulfate solution (25°C, 50°C) in a confined swell test apparatus. Both swell test samples were analyzed by means of X-ray powder diffraction. The peak intensities of newly formed ettringite were more pronounced in the sample tested at 50°C, and swell development was only observed in this sample. Scanning electron microscopy analyses revealed well-crystallized ettringite needles exceeding 40 μm in length for this sample, while ettringite crystals less than 15 μm in length formed in the sample tested at 25°C. Therefore, the results suggest that the quantity of ettringite and the extent of crystallization play a key role in the heave of COPR.     

Phosphate treatment of firing range soils: lead fixation or phosphorus release?

Phosphate treatment of lead (Pb)-contaminated soils relies on the premise that Pb converts to the thermodynamically stable, insoluble mineral class of pyromorphites. Recent research showed that treatment performance is kinetically controlled and strongly dependent on soil pH; this study employed an acidic phosphate (P) form, monobasic calcium phosphate (MCP), to investigate treatment performance of Pb occurring in an alkaline-buffered and an acidic firing range soil. The results of leaching, X-ray powder diffraction (XRPD), and modeling analyses showed that P and Pb dissolution in the alkaline soil and transformation reactions were kinetically controlled, so that: (i) TCLP (toxicity characteristic leaching procedure) and SPLP (synthetic precipitation leaching procedure) results were poor to marginal even at high MCP dosages; (ii) brushite (Ca(HPO(4)).2H(2)O) and cerussite (PbCO(3)) persisted in XRPD patterns; and, (iii) geochemical modeling failed to predict leaching and phase assemblages. In the acidic soil, Pb-P reactions promoted further soil acidification, improved TCLP performance, and generated better agreement with the equilibrium-based model; however, SPLP and modeling results showed that Pb concentrations could not be reduced below 15 microg/L mainly due to the low soil pH. The marginal or inadequate Pb immobilization was observed in both soils despite the elevated MCP dosages, which were well in excess of the pyromorphite stoichiometric ratio (P/Pb = 0.6). Additionally, P leaching concentrations and rates were extremely high (>300 mg/L), under both SPLP and deionized (DI) water extraction conditions, and as predicted by thermodynamic equilibrium. The performance and sustainability of phosphate-based treatment therefore seem questionable.     

Stabilization of Cu-contaminated army firing range soils using waste oyster shells

A stabilization/solidification (S/S) process was used to immobilize Cu in contaminated soils obtained from two army firing ranges sites (A and B) with total Cu concentrations of 520 and 380 mg/kg, respectively. Both waste oyster shells (WOS) and pretreated oyster shells (POS) were used to immobilize Cu in the contaminated soils. Waste oyster shells passing the #10 mesh and #20 mesh were used for the Sites A and B, respectively. WOS- and POS-treated soil samples cured for 28 days were evaluated for Cu leaching by the Korean Standard Leaching Test (KSLT) method. Slurry suspensions were prepared to investigate the Cu immobilization mechanism using X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) energy dispersive X-ray spectroscopy (EDX) analyses. The treatment results showed that the POS treatment was more effective than the WOS treatment of 28 days. For Site A, 10 wt% WOS and 3 wt% POS dosages were required to pass the Korean warning standard of 50 mg/kg, while 10 wt% WOS and 5 wt% POS dosages were required for the Site B treatment. The XRPD and SEM-EDX results showed that Cu immobilization was strongly linked to both CSH/CAH and ettringite. Overall, the POS treatment was effective at immobilizing the Cu in the contaminated soils, very likely due to its CaO content.     

Release of arsenic (As) and lead (Pb) from quicklime-sulfate stabilized/solidified soils under diffusion-controlled conditions

A quicklime-sulfate-based stabilization/ solidification (S/S) process for arsenic (As) and lead (Pb) immobilization was evaluated under “semi-dynamic” leaching conditions. In order to simulate aggressive leaching conditions the semi-dynamic leaching tests was modified by using 0.014 N of acetic solution instead of distilled water. Kaolinite-sand and montmorillonite-sand soil samples were artificially contaminated with As and Pb, compacted and cured for 28 days. The semi-dynamic leaching tests were then conducted for 90 days. The effectiveness of the S/S treatment was evaluated by assessing the cumulative release of As and Pb as well as by determining the diffusion coefficients (D _eff) and leachability indices (LX). The release of As and Pb was greatly reduced by quicklime-sulfate treatment as compared to untreated samples. Moreover, the quicklime-sulfate treatment was more effective than the quicklime-only treatment in reducing both As and Pb release. The controlling leaching mechanisms were determined using a diffusion theory model. Upon S/S treatment, As and Pb release was diffusion controlled. The LX of all the treated samples were greater than nine, suggesting that S/S treated samples were suitable for “controlled utilization”.     

Management of fat reserves in tufted titmice (Parus bicolor ): evidence against a trade-off with food hoards

Caching species can manage their energy supply by adjusting body fat, number of caches, or both. It has been hypothesized that because body fat has a higher fitness cost than caches, small food-hoarding birds respond to increased starvation risk by increasing the number of their caches rather than their fat load. This hypothesis predicts that when birds cannot cache they should compensate for the loss of external energy storage by (1) shifting the time of their daily body mass accumulation toward earlier in the day and (2) increasing the overall level of their fat reserves. During the winter of 1995–1996, we tested these predictions with a caching species, the tufted titmouse (Parus bicolor). Each of six experimental birds was fed a diet of uncachable sunflower seed powder for 6 days, preceded and followed by 6-day control periods during which they were fed cachable sunflower seeds. The daily pattern of body mass gain was unaffected by the opportunity to cache. Furthermore, when unable to cache, the birds did not increase either their mean daily body mass, body mass in the middle of the day, or evening body mass compared to the two control periods. These results argue against the hypothesis of a trade-off between fat reserves and food caches in tufted titmice, and suggest that fat reserves are managed independently of external food caches. Received: 9 April 1997 / Accepted after revision: 30 August 1997