Alexander P. Robertson

Complexation of carbonate species at the goethite surface: Implications for adsorption of metal ions in natural waters

Headspace Pco, was measured with an infrared gas analyzer over an equilibrated goethite suspension to determine adsorption of carbonate species in the pH range 3 to 8. For a 2 g/L goethite suspension in 0.1 N NaC104 (-3 1O-4 M surface sites), the fraction of carbonate species adsorbed increased from 0.15 at pH 3 to a maximum of 0.56 at pH 6. In 0.0 1 N NaC104, the fraction of carbonate species adsorbed at pH 6 increased to 0.67. The total concentration of CO2 in the suspension increased from about 0.4 to 0.6 1O-4 M in the pH range of these experiments. The development of surface charge at the goethite surface was determined in the pH range 4 to 11 by potentiometric titration under controlled low CO2 conditions. No hysteresis was observed between the acid and base legs of titrations in 0.10,0.03, and 0.01 N NaC104 resulting in a pH,,, of 8.9. The carbonate species adsorption data were modelled using the least squares optimization program FITEQL for the diffuse double-layer model and the triple- layer model using stoichiometries of the type Fe-OCOOH and Fe-OCOO for surface bound carbonate species. The model results are consistent with separate experiments showing a significant reduction in chromate adsorption on goethite as the partial pressure of CO* was increased from <5 to 450 and 40,000 patm. Our data suggest that mineral oxide surface sites which control solid/solute partitioning of metal ions in natural systems may be largely bound to adsorbed carbonate species.

Acid/base, copper binding, and Cu2+/H+ exchange properties of a soil humic acid, an experimental and modeling study

Acid/base, copper binding and proton exchange properties of a soil humic acid were studied over a range of pHs and ionic strengths. Results indicate that multiple classes of copper binding sites exist. A number of model formulations were used to simulate the data; none were able to reasonably match all aspects of the observed behavior. Model results and analyses suggest that successful replication of humic behavior over a wide range of conditions requires a model formulation which incorporates electrostatic effects for a variable geometry entity, multiple site classes, and probably both uni and multi dentate complexation. Additionally site heterogeneity estimates from acid/base titration data are not likely to reasonably assess the presence of low concentration, high (metal) affinity sites that can be relevant in the study of trace metal complexation.

Video methods in the quantification of children's exposures

In 1994, Stanford Universitys Exposure Research Group (ERG) conducted its first pilot study to collect micro-level activity time series (MLATS) data for young children. The pilot study involved videotaping four children of farm workers in the Salinas Valley of California and converting their videotaped activities to valuable text files of contact behavior using video-translation techniques. These MLATS are especially useful for describing intermittent dermal (i.e., second-by-second account of surfaces and objects contacted) and non-dietary ingestion (second-by-second account of objects or hands placed in the mouth) contact behavior. Second-by-second records of children contact behavior are amenable to quantitative and statistical analysis and allow for more accurate model estimates of human exposure and dose to environmental contaminants. Activity patterns data for modeling inhalation exposure (i.e., accounts of microenvironments visited) can also be extracted from the MLATS data. Since the pilot study, ERG has collected an immense MLATS data set for 92 children using more developed and refined videotaping and video-translation methodologies. This paper describes all aspects required for the collection of MLATS including: subject recruitment techniques, videotaping and video-translation processes, and potential data analysis. This paper also describes the quality assurance steps employed for these new MLATS projects, including: training, data management, and the application of interobserver and intraobserver agreement during video translation. The discussion of these issues and ERGs experiences in dealing with them can assist other groups in the conduct of research that employs these more quantitative techniques.

Effects of long‐range electrostatic forces on simulated protein folding kinetics

Molecular dynamics simulations are a useful tool for characterizing protein folding pathways. There are several methods of treating electrostatic forces in these simulations with varying degrees of physical fidelity and computational efficiency. In this article, we compare the reaction field (RF) algorithm, particle‐mesh Ewald (PME), and tapered cutoffs with increasing cutoff radii to address the impact of the electrostatics method employed on the folding kinetics. We quantitatively compare different methods by a correlation of quantitative measures of protein folding kinetics. The results of these comparisons show that for protein folding kinetics, the RF algorithm can quantitatively reproduce the kinetics of the more costly PME algorithm. These results not only assist the selection of appropriate algorithms for future simulations, but also give insight on the role that long‐range electrostatic forces have in protein folding.

Controlled field studies on soil aquifer treatment in a constructed coastal sandfill

A controlled artificial recharge experiment was conducted to investigate the effect of soil aquifer treatment during percolation of secondary and tertiary (ultrafiltered) treated wastewater through the shallow vadoze zone of a newly constructed coastal sandfill. The sandfill is a reclaimed land constructed from marine sand dredged from the seabed. To obtain 1-D flow, a stainless steel column was driven to a depth of 2.5 m, penetrating the phreatic surface. Wastewater was percolated through the column under fully-saturated and unsaturated conditions. Infiltration rates, dissolved organic carbon (DOC) and ultra-violet absorption (UVA) were monitored. The wastewaters were recharged at similar infiltration rates of approximately 5.5 m/day and 3.5 m/day under fully-saturated and unsaturated conditions, respectively. In both cases, clogging occurred 40 days after the start of recharge, under saturated conditions. For secondary treated wastewater, DOC concentration (mg/l) reduced by 28% and 13% under unsaturated and saturated conditions, respectively. The corresponding UVA reduction was 19.4% and 14.1%. Similar reductions in DOC were observed for the tertiary treated wastewater; however, the reduction in UVA was higher; 28% and 22% under unsaturated and saturated conditions, respectively. On an mass removal (mg/m(2) DOC) basis, DOC reduction appeared to be more significant under unsaturated conditions. This is attributed to the presence of interstitial oxygen.

DOC and UVA attenuation with soil aquifer treatment in the saturated zone of an artificial coastal sandfill

Results from a direct recharge experiment conducted in the field to investigate DOC and UVA(254) attenuation rates during the direct injection of UF treated wastewater into a artificial coastal sandfill are presented in this paper. Approximately 500 m(3) of ultra-filtered wastewater was injected into the saturated zone, over a period of 9 days. The movement of the plume was tracked over 80 days, during which time samples were obtained from multilevel samplers installed in transects across the drift axis of the plume. An analysis of fluorescein in the samples obtained during the drift of the UF plume showed that DOC and UVA were attenuated beyond rates predicted by conservative mixing, by up to a maximum of 45%. A degradation coefficient of 0.0175 day(-1) was found to be applicable for DOC degradation. After a drift period of 80 days, DOC and UVA reduced to approximately 4.5 mg/l and 0.100 cm(-1), respectively, from initial values of 8.06 mg/l and 0.199 cm(-1).

Geochemical changes during recharge with tertiary-treated wastewater at a coastal sandfill

Results of experiments investigating geochemical changes during artificial recharge of treated wastewater at a coastal sandfill, reclaimed with sand dredged from the seabed, are reported in this paper. Laboratory batch experiments were conducted using secondary effluent (SE) and SE treated with an additional ultrafiltration process (UF), and wastewater treated by reverse osmosis (RO) process, mixed with surface sand obtained from the sandfill. Experiments with RO showed a net increase of 0.41 meq/L, 0.12 meq/L and 0.31 meq/L for Ca(2 + ), Mg(2 + ) and HCO(3) (-), respectively. UF and SE also exhibited net increase in Ca(2 + ), Mg(2 + ) and HCO(3) (-) indicating carbonate mineral dissolution. All three waters were found to be over-saturated with respect to calcite. Carbonate dissolution reactions were observed in the field experiments. However, the presence of imported clays from the borrow source gave rise to ion exchange reactions where Na(+) attached to the clay particles were exchanged for Ca(2 + ) and Mg(2 + ) inducing mineral dissolution, driven by sub-saturation conditions. This resulted in an increase in pH with maximum values in excess of 9.0. It was also found that the sodium adsorption ratio remained high (>10) even after the groundwater had been diluted sufficiently to freshwater levels (ionic strength, I <0.015) indicating a potential for the dispersion of clay particles. This could have a deleterious consequence on porosity and hydraulic conductivity.