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C E Martínez

Publications and source records attributed to C E Martínez.

6 recordsLinked to original sources

Thermally induced changes in metal solubility of contaminated soils is linked to mineral recrystallization and organic matter transformations.

Soils are biogeochemical systems under continual modification by biological and chemical processes. Trace element solid-solution partitioning is thus influenced by long-term changes to these solid phases. We study Pb, Cd, Zn, and Cu solution speciation and solid-phase dynamics in two soils of volcanic origin (Te Akatea and Egmont, high in noncrystalline aluminosilicates), an oxisol from Brazil (Oxisol, high in oxides of Al and Fe), and several sludge-treated soils (labeled NYS soils, high in organic materials). Total soluble (by ICP) and labile (by ASV) concentrations of Pb, Cd, Zn, and Cu were determined after incubation of the soils for about 1.5 yr at room (23 degrees C) and elevated (70 degrees C) temperatures. Changes occurring to the solid phases were monitored by FTIR and extraction with oxalate and pyrophosphate. It is shown that induced hydrolysis or decomposition of organic materials in soils results in increases in both labile and total soluble concentrations of Pb, Cd, Cu, and Zn in solution. Labile and total soluble concentrations of Cu and Zn increase concomitantly with dissolved organic carbon (DOC); the nonlabile soluble fraction also increases with increasing DOC. Similarly, the concentration of Cd and Pb in solution increases with increasing DOC; however, most soluble Cd and Pb is asv-labile. Only in the Egmont soil (mineralogy dominated by proto-imogolite allophane) was reduced Pb solubility observed after prolonged equilibration and heating. Lead solubility increased after partial crystallization of amorphous minerals in the Te Akatea and the Oxisol. Thus, for most of the metal-soil systems studied, prolonged thermal treatment at 70 degrees C increased total soluble and asv-labile metals, suggesting that aging effects on metals in contaminated soils could release metals to labile forms in some cases.

Metals, Heavy↗

Cd, Cu, Pb, and Zn coprecipitates in Fe oxide formed at different pH: aging effects on metal solubility and extractability by citrate.

Coprecipitates of heavy metals with Fe oxides may form in contaminated soil, water, and sediment systems, particularly when oxidation-reduction processes are occurring. Once formed, coprecipitates with ferrihydrite could limit heavy metal mobility, solubility, toxicity, and bioavailability in geochemical systems. In this study, Cd, Cu, Pb, and Zn were coprecipitated with Fe by titration to pHs 6 and 7. Metal solubility was monitored during the coprecipitation process to pH 7 and after aging of the product. In the coprecipitate formed at pH 6, metal solubility was determined after the system reached pH 6 and at subsequent time intervals. We also reacted the coprecipitates with citrate and evaluated potential metal availability at increased aging times. The pH of coprecipitate formation had little effect on the long-term solubility of Cu and Zn, whereas soluble Cd was greater in the coprecipitate formed at pH 6. Soluble percentages of metals were low at both pH 6 and 7 for Cu and Pb but averaged 1.5 to 3% for Zn and greater than 40% for Cd. Hysteresis was observed in the coprecipitation curves for Zn and Cd, revealing reduced solubility after adsorption or coprecipitation. Lead and Cu failed to show hysteresis, with strong retention in the solid phase at pH greater than 6. The citrate-extractable fraction was greatest for Cd and Zn, less for Cu, and least for Pb. Citrate-extractable metal was higher for the coprecipitate formed at pH 7 than at pH 6, suggesting increased potential availability from coprecipitates formed at higher pH.

Citrates↗

Solubility of lead, zinc and copper added to mineral soils.

Elevated levels of heavy metals in soils are a result of industrial activities, atmospheric deposition, and the land application of sewage sludges and industrial by-products. Their persistence in the soil environment has created interest in the possible changes in solubility. In this study, total dissolved concentrations of Pb, Zn, and Cu were monitored in seven metal-amended soils (a calcareous and six acid mineral soils). Single metal solutions were added to soils and equilibrated (aged) for 40 days. During the 40 days the soil was allowed to air-dry and was rewetted in cycles of about 5 days. At the end of this reaction period, metal solubility was measured (by atomic absorption spectrometry and direct current plasma spectrometry) at the initial soil pH and at decreased pH values which were induced by addition of small aliquots of acid. As expected, solubility of added Pb, Zn, and Cu increased with a decrease in pH. Furthermore, the results showed that the solubility relationship with pH was similar in all non-calcareous soils. This suggests that metal solubility may be controlled by similar soil components, presumably involving soil characteristics such as pH, organic matter content, and soil mineralogy. For each metal, an approximate pH value was found at which solubility deviated from the solubility of metals when they occur in soils at typical (natural) values. This pH was about (pH+/-0.2): 5.2 for Pb, 6.2 for Zn, and 5.5 for Cu. Thus, pH values below these thresholds may enhance metal mobility, biological availability and toxicity in soils. Metals dissolved at higher pH in the calcareous soil (18.8 g kg(-1) inorganic carbon, initial pH 8.2). In a calcareous soil, a significant fraction of these metals react with carbonates, and decreased pH results in much higher metal dissolution. Yet, metal solubility in soils is not determined by the formation and dissolution of single metal compounds.

Journal Article↗

Effect of pupillary dilation on corneal optical aberrations after photorefractive keratectomy.

BACKGROUND: Complaints of glare, halos, and disturbances of night vision after photorefractive keratectomy (PRK) probably result from changes in the corneal aberration structure induced by the laser ablation procedure. The purpose of this article is to characterize changes in the corneal aberration structure after PRK and to demonstrate the effect of pupil dilation on these changes. METHODS: Videokeratographs obtained preoperatively (n = 112) and at 1 (n = 94), 3 (n = 103), 6 (n = 91), 12 (n = 60), 18 (n = 53), and 24 (n = 44) months postoperatively from 112 eyes of 89 patients who had undergone PRK for myopia were analyzed. The data were used to calculate the wavefront variance of the cornea for both small (3-mm) and large (7-mm) pupils. RESULTS: For both the 3- and 7-mm pupil, coma-like aberrations increased significantly from preoperative values to 1-month postoperative values (P < .05 and P < .001, respectively); for 7-mm pupils, the postoperative values never returned to preoperative values (P < .001, 24 months). For the 3-mm pupil, spherical-like aberrations decreased significantly 1 month after surgery (P < .001), and never returned to preoperative values. For the 7-mm pupil, spherical-like aberrations increased significantly 1 month after surgery (P < .001) and did not return to preoperative values. Opening the pupil from 3 to 7 mm increased spherical-like aberrations only 7-fold before PRK. After PRK, however, pupillary dilation caused a 300-fold increase in this type of aberration. For both pupil sizes at all times after PRK, the magnitude of the surgically induced aberration correlated with the amount of the attempted correction (P < .001, r2 = 0.6 at 1 month for a 7-mm pupil). CONCLUSIONS: Photorefractive keratectomy increases the wavefront variance of the cornea; PRK changes the relative contribution of coma-like and spherical-like aberrations; after PRK, the diameter of the entrance pupil greatly affects the amount and character of the aberrations; and the magnitude of the aberration increases with the attempted correction. CLINICAL RELEVANCE: Quantitative characterization of irregular astigmatism with the measurement of aberration structures following corneal surgery and the correlation of these data with visual performance in clinical trials provide the basis for understanding patient complaints and for improving surgical approaches. Our analysis shows that, whereas induced aberrations are minimal for simulated day-time vision (3-mm pupil), the increase in aberrations measured for simulated night vision (7-mm pupil) supports the use of large treatment zones to reduce visual disturbances such as glare and halos.

Adult↗