A sustainable sulfate process to produce TiO2 pigments

Titanium dioxide (TiO₂) is a widely used white pigment. TiO₂ production in 2006 was about 1,400,000 metric tons in the USA. The two major processes to manufacture TiO₂ are the chloride process and the sulfate process. Currently, the TiO₂ industry finds the waste generated in the chloride process less than the waste generated in the sulfate process in its present design, despite generating large quantities of process-related carbon dioxide and carbon monoxide. As a consequence, the sulfate process appears less economical, notably due to the production of green vitriol, FeSO₄·7H₂O, as a major waste. Here, we describe a more sustainable sulfate process based on an earlier study on thermal decomposition of iron(II) sulfates. In the sustainable sulfate process, FeSO₄·7H₂O waste is used for greener production of sulfuric acid, H₂SO₄, used in turn for the digestion of ilmenite. Theoretical and actual yields of waste byproducts per metric ton of TiO₂ produced are used to show the environmental and economic advantages of the sustainable sulfate process.     

Leader self‐awareness: An examination and implications of women's under‐prediction

Self‐awareness represents an important aspect of leadership. However, past research on leader self‐awareness has focused on one component of self‐awareness, self versus others' ratings, leaving the second component, the ability to anticipate the views of others, largely neglected. We examined this second component of self‐awareness by focusing on women leaders who have been found to under‐predict how others rate them. In two studies, we measured how women leaders anticipate the views of their bosses in regard to their leadership. In Study 1, 194 leaders rated their leadership, were rated by their bosses, and then predicted how their bosses rated their leadership. While we found that women under‐predict their boss ratings compared with men, we did not find that boss gender or feedback played a role in this under‐prediction. In Study 2, 76 female leaders identified (via open‐ended questions) possible reasons and consequences of under‐prediction for women in organizations. Results from Study 2 reveal the following: (1) the reasons for women's under‐prediction include a lack of self‐confidence, differences in feedback needs, learned gender roles, and self‐sexism; and (2) the perceived consequences of under‐prediction are negative for both women and the organization. Copyright © 2013 John Wiley & Sons, Ltd.     

Microbial responses to combined oxidation and catalysis treatment of 1,4-dioxane and co-contaminants in groundwater and soil

Post-treatment impacts of a novel combined hydrogen peroxide (H₂O₂) oxidation and WO_x/ZrO₂ catalysis used for the removal of 1,4-dioxane and chlorinated volatile organic compound (CVOC) contaminants were investigated in soil and groundwater microbial community. This treatment train removed ~90% 1,4-dioxane regardless of initial concentrations of 1,4-dioxane and CVOCs. The Illumina Miseq platform and bioinformatics were used to study the changes to microbial community structure. This approach determined that dynamic shifts of microbiomes were associated with conditions specific to treatments as well as 1,4-dioxane and CVOCs mixtures. The biodiversity was observed to decrease only after oxidation under conditions that included high levels of 1,4-dioxane and CVOCs, but increased when 1,4-dioxane was present without CVOCs. WO_x/ZrO₂ catalysis reduced biodiversity across all conditions. Taxonomic classification demonstrated oxidative tolerance for members of the genera Massilia and Rhodococcus, while catalyst tolerance was observed for members of the genera Sphingomonas and Devosia. Linear discriminant analysis effect size was a useful statistical tool to highlight representative microbes, while the multidimensional analysis elucidated the separation of microbiomes under the low 1,4-dioxane-only condition from all other conditions containing CVOCs, as well as the differences of microbial population among original, post-oxidation, and post-catalysis states. The results of this study enhance our understanding of microbial community responses to a promising chemical treatment train, and the metagenomic analysis will help practitioners predict the microbial community status during the post-treatment period, which may have consequences for long-term management strategies that include additional biodegradation treatment or natural attenuation.

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Use of macroinvertebrate assemblages for assessing performance of stabilization ponds treating effluents from sugarcane and molasses processing

Wastewater discharge from sugarcane processing is a significant pollutant of tropical aquatic ecosystems. For most developing countries, monitoring of the level of pollutants is done mostly through chemical analysis, but this does not reflect potential impacts on aquatic assemblages. In addition, laboratory facilities for accurate concentration measurements are often not available for regular monitoring programs. In this study, we investigated the use of benthic macroinvertebrates for biological monitoring in western Kenya. Benthic macroinvertebrates were sampled in stabilization ponds treating wastewater from sugarcane- and molasses-based processing plants to assess their composition and abundance in relation to different concentrations of chemical variables. Optimum concentrations and tolerance values were identified for various taxa, and a biotic index was developed that combined tolerance values (ranked between 0 and 10) for the various macroinvertebrate taxa. A succession in composition and distribution of macroinvertebrate taxa was observed from the inlet to the outlet of the pond systems. Diptera dominated in the first ponds that had high concentrations of chemical oxygen demand (COD), biological oxygen demand (BOD₅), and nutrients, while intolerant Ephemeroptera, Plecoptera, and Trichoptera (EPT) appeared as the concentrations dropped in subsequent ponds. The effluent quality was classified as “good,” “fair,” and “poor,” corresponding with biotic index value ranges 0–3.50, 3.51–6.50, and 6.51–10, respectively. During validation, the index grouped sites with respect to levels of measured environmental variables. The study revealed that the developed biotic index would help in monitoring the quality of sugarcane processing and molasses effluents before release into recipient aquatic ecosystems, replacing the need for costly chemical analyses.     

Assessment of the functionality of a pilot-scale reactor and its potential for electrochemical degradation of calmagite, a sulfonated azo-dye

Electrochemical degradation (ECD) is a promising technology for in situ remediation of diversely contaminated environmental matrices by application of a low level electric potential gradient. This investigation, prompted by successful bench-scale ECD of trichloroethylene, involved development, parametric characterization and evaluation of a pilot-scale electrochemical reactor for degradation of calmagite, a sulfonated azo-dye used as a model contaminant. The reactor has two chambers filled with granulated graphite for electrodes. The system has electrical potential, current, conductivity, pH, temperature, water-level and flow sensors for automated monitoring. The reactor supports outdoor and fail-safe venting, argon purging, temperature regulation and auto-shutdown for safety. Treatment involves recirculating the contaminated solution through the electrode beds at small flow velocities mimicking low fluid-flux in groundwater and submarine sediments. The first phase of the investigation involved testing of the reactor components, its parametric probes and the automated data acquisition system for performance as designed. The results showed hydraulic stability, consistent pH behavior, marginal temperature rise (<5 degrees C) and overall safe and predictable performance under diverse conditions. Near complete removal of calmagite was seen at 3-10V of applied voltage in 8-10h. The effects of voltage and strength of electrolyte on degradation kinetics have been presented. Further, it was observed from the absorption spectra that as calmagite degrades over time, new peaks appear. These peaks were associated with degradation products identified using electrospray ionization mass spectrometry. A reaction mechanism for ECD of calmagite has also been proposed.     

Simple Modeling Tool for Reconstructing Source History Using High Resolution Contaminant Profiles From Low‐k Zones

An innovative but simple analytical modeling tool for reconstructing contaminant concentration versus time trends (i.e., “source history”) for a site using high‐resolution contaminant profiles from low permeability (low‐k) zones was developed and tested. Migration of contaminants into low‐k zones via diffusion (and possibly slow advection) produce concentration versus depth profiles that can be used to understand temporal concentration trends at the interface with overlying transmissive zones, including evidence of attenuation over time due to source decay. A simple transport‐based spreadsheet tool for generating source history estimates fit to the profiles was developed and applied to published soil concentration versus depth data from five distinct areas of four different sites contaminated with chlorinated ethenes. Using the root mean square error as an optimization metric, strong fits between measured and model‐predicted soil data were obtained in the majority of cases using site‐specific values for input parameters. In general, significant improvements could not be obtained by varying these parameters. As a result, the source history estimates generated by the tool were similar to those that had already been generated using more intensive analytical or numerical inverse modeling approaches. This included confirmation of constant source histories at locations where dense nonaqueous‐phase liquid was present (or suspected to be present), and declining source histories for locations where source isolation and/or attenuation had occurred. The advantage of the modeling tool described here is that it provides a simpler yet more dynamic method for understanding source behavior over time than existing approaches. ©2015 Wiley Periodicals, Inc.     

Measuring the environmental performance of IPPC industry: I. Devising a quantitative science-based and policy-weighted Environmental Emissions Index

This paper describes the derivation of an Environmental Emissions Index (EEI) intended to quantify the environmental performance of Integrated Pollution Prevention and Control (IPPC) installations and sectors. Characterisation and normalisation methods used in lifecycle analyses were applied to 20 routinely reported emissions parameters, pertaining to six environmental impact categories. Distance to policy targets for relevant emissions were used to weight impact categories, and link the EEI to policy priorities. Ireland and the EU15 were considered as scales of context. The European Pollutant Emission Register was a convenient source of normalisation data, but restricted the context of the EEI to industrial emissions, and distorted outputs. Using national and EU15 total loading estimates for normalisation resulted in an EEI that better reflected the relative contribution of reported emissions towards overall environmental pressures. Using Ireland's pharmaceutical sector as a case study indicated that weighting factors, and the toxicity range of NMVOC emissions, were the largest sources of EEI uncertainty. Through the integration of inventory data, scientific characterisation, and policy targets, the EEI translates reported emissions data from IPPC installations and sectors into a benchmark of environmental performance. It may be regarded as an evolving tool of potential utility to regulators and policy makers.