Similar retardation of arsenic in gray Holocene and orange Pleistocene sediments: Evidence from field-based column experiments in Bangladesh.

Groundwater flow has the potential to introduce arsenic (As) in previously uncontaminated aquifers. The extent to which As transport is retarded by adsorption is particularly relevant in Bangladesh where low-As wells offer the best chance of reducing chronic exposure to As of a large rural population dependent on groundwater. In this study, column experiments were conducted with intact cores in the field to measure As retardation. Freshly collected cores of reduced iron (Fe-II) dominated gray sediment of Holocene age as well as oxidized Fe (III)-coated orange sediment of Pleistocene age were eluted at pore-water velocities of 40-230 cm/day with anoxic groundwater pumped directly from a well and containing 320 µg/L As. Up to 100 µg/L As was immediately released from gray sand but the main As breakthrough for both gray and orange sand occurred between 30 and 70 pore volumes, depending on flow rate. The early release of As from gray sand is attributed to the presence of a weakly bound pool of As. The sorption of As was kinetically limited in both gray and orange sand columns. We used a reversible multi-reaction transport model to simulate As breakthrough curves while keeping the model parameters as constant as possible. Contrary to the notion that dissolved As is sorbed more strongly to orange sands, we show that As was similarly retarded in both gray and orange sands in the field.

Highly bioavailable dust-borne iron delivered to the Southern Ocean during glacial periods.

Changes in bioavailable dust-borne iron (Fe) supply to the iron-limited Southern Ocean may influence climate by modulating phytoplankton growth and CO2 fixation into organic matter that is exported to the deep ocean. The chemical form (speciation) of Fe impacts its bioavailability, and glacial weathering produces highly labile and bioavailable Fe minerals in modern dust sources. However, the speciation of dust-borne Fe reaching the iron-limited Southern Ocean on glacial-interglacial timescales is unknown, and its impact on the bioavailable iron supply over geologic time has not been quantified. Here we use X-ray absorption spectroscopy on subantarctic South Atlantic and South Pacific marine sediments to reconstruct dust-borne Fe speciation over the last glacial cycle, and determine the impact of glacial activity and glaciogenic dust sources on bioavailable Fe supply. We show that the Fe(II) content, as a percentage of total dust-borne Fe, increases from ∼5 to 10% in interglacial periods to ∼25 to 45% in glacial periods. Consequently, the highly bioavailable Fe(II) flux increases by a factor of ∼15 to 20 in glacial periods compared with the current interglacial, whereas the total Fe flux increases only by a factor of ∼3 to 5. The change in Fe speciation is dominated by primary Fe(II) silicates characteristic of glaciogenic dust. Our results suggest that glacial physical weathering increases the proportion of highly bioavailable Fe(II) in dust that reaches the subantarctic Southern Ocean in glacial periods, which represents a positive feedback between glacial activity and cold glacial temperatures.

High particulate iron(II) content in glacially sourced dusts enhances productivity of a model diatom.

Little is known about the bioavailability of iron (Fe) in natural dusts and the impact of dust mineralogy on Fe utilization by photosynthetic organisms. Variation in the supply of bioavailable Fe to the ocean has the potential to influence the global carbon cycle by modulating primary production in the Southern Ocean. Much of the dust deposited across the Southern Ocean is sourced from South America, particularly Patagonia, where the waxing and waning of past and present glaciers generate fresh glaciogenic material that contrasts with aged and chemically weathered nonglaciogenic sediments. We show that these two potential sources of modern-day dust are mineralogically distinct, where glaciogenic dust sources contain mostly Fe(II)-rich primary silicate minerals, and nearby nonglaciogenic dust sources contain mostly Fe(III)-rich oxyhydroxide and Fe(III) silicate weathering products. In laboratory culture experiments, Phaeodactylum tricornutum, a well-studied coastal model diatom, grows more rapidly, and with higher photosynthetic efficiency, with input of glaciogenic particulates compared to that of nonglaciogenic particulates due to these differences in Fe mineralogy. Monod nutrient accessibility models fit to our data suggest that particulate Fe(II) content, rather than abiotic solubility, controls the Fe bioavailability in our Fe fertilization experiments. Thus, it is possible for this diatom to access particulate Fe in dusts by another mechanism besides uptake of unchelated Fe (Fe') dissolved from particles into the bulk solution. If this capability is widespread in the Southern Ocean, then dusts deposited to the Southern Ocean in cold glacial periods are likely more bioavailable than those deposited in warm interglacial periods.

Estimation of reactive thiol concentrations in dissolved organic matter and bacterial cell membranes in aquatic systems.

Organic thiols are highly reactive ligands and play an important role in the speciation of several metals and organic pollutants in the environment. Although small thiols can be isolated and their concentrations can be estimated using chromatographic and derivatization techniques, estimating concentrations of thiols associated with biomacromolecules and humic substances has been difficult. Here we present a fluorescence-spectroscopy-based method for estimating thiol concentrations in biomacromolecules and cell membranes using one of the soluble bromobimanes, monobromo(trimethylammonio)bimane (qBBr). The fluorescence of this molecule increases significantly when it binds to a thiol. The change in the sample fluorescence due to thiols reacting with qBBr is used to determine thiol concentration in a sample. Using this method, small thiols such as cysteine and glutathione can be detected in clean solutions down to ~50 nM without their separation and prior concentration. Thiols associated with dissolved organic matter (DOM) can be detected down to low micromolar concentration, depending on the DOM background fluorescence. The charge on qBBr prevents its rapid diffusion across cell membranes, so qBBr is ideal for estimating thiol concentration at the cell membrane-water interface. This method was successfully used to determine the thiol concentration on the cell envelope of intact Bacillus subtilis to nanomolar concentration without any special sample preparation. Among the chemical species tested for potential interferences (other reduced sulfides methionine and cystine, carboxylate, salt (MgCl(2))), carboxylates significantly influenced the absolute fluorescence signal of the thiol-qBBr complex. However, this does not affect the detection of thiols in heterogeneous mixtures using the presented method.

Evaluation of a mental skills program for serving for an intercollegiate volleyball team.

A preseason mental skills program for serving was implemented for the 11 members of an intercollegiate volleyball team (M age = 20.0 yr.; SD = 1.1; years of intercollegiate volleyball experience M = 2.6; SD = 0.9). Key mental skills taught were relaxation, imagery, attentional focus, goal setting, behavioral modeling, and performance routine. A videotaped behavioral model articulated and demonstrated technical performance keys to effective serving. Players utilized a three-phase service routine to increase automaticity of performance and to incorporate key mental skills. End-of-season reported use of imagery was significantly correlated with Good Serve Percentage, as was reported use of a service routine. The mean Good Serve Percentage for the season was 49% (SD=7); the team goal was 50%. Serve-specific self-efficacy significantly increased from the pretraining program to the end of the season. Results indicated that implementing the mental skills training program was associated with enhanced service performance.

A laboratory study of satisfaction effects on mood state, withdrawal intentions, and organizational citizenship behavior.

154 undergraduates role-played a restaurant server experiencing positive, neutral, or negative Job or Life Satisfaction. Positive Satisfaction resulted in ratings of more positive reported mood state, lower expected absenteeism and turnover intentions, and greater expected Organizational Citizenship Behavior than did Neutral Satisfaction and Negative Satisfaction. Life Satisfaction was associated with reported mood states and intentions similarly to Job Satisfaction, except Negative Job Satisfaction was more negatively influential on expectations of quitting than Negative Life Satisfaction. Both Job and Life Satisfaction may be antecedents to affect and its consequences in work settings.

Comparison of constant and variable practice conditions on free-throw shooting.

The proposition that variable practice may be superior to constant practice even for consistent transfer situations was tested on a prototypical consistently performed skill, the basketball free throw. 94 participants were matched on free-throw shooting, then randomly assigned to one of four practice conditions, a Constant condition, i.e., at the free-throw line, and three Variable conditions. Under supervision participants practiced shooting free throws four days a week for three weeks. Three substantially different variable practice conditions produced significant improvement similar to that of constant practice on tests during each week of practice and on a delayed retention test. Consistent with the proposition, the most variable practice group performed as well as the other groups on the retention test despite lower practice performance.