Endocrine-disrupting substances: I. Relative risks of PFAS in drinking water.

Concentrations of per and polyfluorinated alkyl substances (PFAS) in drinking water are significantly lower than in vivo levels of the native target hormone. These concentrations are orders of magnitude lower than the hormone in question, particularly when corrected for transactivation. A pregnant woman can excrete about 7,000 µg/day of total estrogens. A low-dose oral contraceptive pill contains 20 µg estradiol. Soy-based baby formula contains phytoestrogens equivalent to a low-dose oral contraceptive pill. A woman on a low-dose oral hormone replacement therapy consumes about 0.5-2 mg/day of one or more estrogens. The levels of endocrine-disrupting substances (EDSs) exposure by oral, respiratory, or dermal routes have the potential to make removing PFAS from drinking water due to its estrogenic activity divert valuable resources. These levels become even less of a threat when their estrogenic potencies are compared with those of the target hormones present as contaminants in water and even more so when compared with levels commonly present in human tissues. The fact that PFAS constitute a tiny fraction compared to exposure to phytoestrogens makes the effort even more insignificant. If PFAS are to be removed from drinking water, it is not due to their estrogenic activity.

Improving safe sanitation practices using groundwater transport modelling and water quality monitoring data.

In many developing countries, poorly constructed pit latrines are the primary source of groundwater contamination. Approaches are needed to identify site-specific separation distances between domestic wells and pit latrines. In this study, tracer transport simulations are combined with water quality monitoring data to identify separation distances in peri-urban Dar es Salaam. Bivariate correlation and linear regression models were used to find the relationships between (1) simulated tracer and distances from the wells to the nearest pit latrines (2) simulated tracer and observed contaminants (nitrate, E. coli, and total dissolved solids). The results showed a strong correlation between tracer with nitrate and E. coli, with Pearson coefficient (r) values of 0.80 and 0.79, but a weak correlation with total dissolved solids (TDS) (r = 0.23). A strong correlation between tracer and distance for shallow and deep wells (r = -0.96, -0.76) was found. Based on the soil type and aquifer properties in the area, wells must be placed at least 34 m from a pit latrine to minimize contamination. With recent advances in sensor technologies and the availability of low-cost sensors, linking simulated tracer with observed contaminant levels may provide an alternative first approach to quickly assess human health risks associated with groundwater contamination.

Global Environmental Engineering for and with Historically Marginalized Communities.

Marginalized communities lack full participation in social, economic, and political life, and they disproportionately bear the burden of environmental and health risks. This special issue of Environmental Engineering Science, the official journal of the Association of Environmental Engineering and Science Professors (AEESP), reports research on the unique environmental challenges faced by historically marginalized communities around the world. The results of community-based participatory research with an Afro-descendant community in Columbia, Native American communities in Alaska, United States, villagers in the Philippines, disadvantaged communities in California, United States, rural communities in Mexico and Costa Rica, homeless encampments in the San Diego River (United States) watershed entrepreneurs in Durban, South Africa, and remote communities in the island nation of Fiji are presented. The research reported in this special issue is transdisciplinary, bringing engineers together with anthropologists, sociologists, economists, and public health experts. In the 13 articles in this special issue, some of the topics covered include inexpensive technologies for water treatment, novel agricultural strategies for reversing biodiversity losses, and strategies for climate change adaptation. In addition, one article covered educational strategies for teaching ethics to prepare students for humanitarian engineering, including topics of poverty, sustainability, social justice, and engineering decisions under uncertainty. Finally, an article presented ways that environmental engineering professors can engage and promote the success of underrepresented minority students and enable faculty engaged in community-based participatory research.

Comparison of the photocatalytic efficacy and environmental impact of CdS, ZnFe2O4, and NiFe2O4 under visible light irradiation.

Three photocatalysts (CdS, ZnFe2O4, and NiFe2O4) were synthesized and their ability to photodegrade methylene blue (MB) was evaluated. MB was degraded by both spinel photocatalysts under visible light at room temperature, although their efficacy was less than that for CdS. The photocatalytic efficacies of NiFe2O4 were observed to be much greater than that for ZnFe2O4. All the synthesized nanoparticles absorbed visible light, while CdS had a larger absorption range within the visible light spectra and the most porous surface. Photo-deactivation was observed during the study, which could be due to the chemical adsorption of the degraded products on the catalyst surface. The factors that affected MB removal efficacy include the absorption range of photocatalysts, initial MB concentrations, amount of photocatalysts added, and photoreactor conditions. Life cycle analysis was used to compare the preparation methods of the photocatalysts in terms of energy consumption and environmental impact. The results showed that the hydrothermal method for NiFe2O4 preparation was less energy-intensive than the sol-gel method for CdS and ZnFe2O4 as the hydrothermal method is effective over a wider range of temperatures in aqueous media. Also, as ZnFe2O4, and NiFe2O4 have lower environmental impacts than CdS both show promise as photocatalysts.

Impact of domestic wells and hydrogeologic setting on water quality in peri-urban Dar es Salaam, Tanzania.

In densely populated urban areas of many low-income countries, water scarcity, poor water quality, and inadequate wastewater management present complex challenges to ensuring health and wellbeing. This study was conducted in an impoverished peri-urban community in Dar es Salaam, Tanzania that experiences water scarcity and relies on domestic wells for drinking water. The objective of this study was to identify the sources of domestic well water contamination and assess the relationship and association of water contamination with three variables 1) the proximity of the well to a sanitation system, 2) well age, and 3) well depth. Out of the 71 wells tested, samples from >80% of wells contained Escherichia coli (E. coli) and 58% had nitrate levels above WHO guidelines. The average concentration of total dissolved solids (TDS) was 882 mg/L, which exceeded the WHO guideline of 600 mg/L. Bivariate correlation analysis showed a strong correlation between water contamination and proximity of the well to a sanitation system along with well depth. Univariate regression analysis confirmed the association of contaminants with distance of a well from a sanitation system and well depth (p < 0.05) but age of the well did not show any significant influence on water quality. Our findings indicate significant contamination of wells from nearby septic tanks and pit latrines. New regulatory mandates for the distance of domestic wells from sanitation systems are essential to prevent groundwater contamination and to protect human health.

Rejection of Bromide and Bromate Ions by a Ceramic Membrane.

Effects of pH and the addition of calcium chloride (CaCl(2)) on bromate (BrO(3) (-)) and bromide (Br(-)) rejection by a ceramic membrane were investigated. Rejection of both ions increased with pH. At pH 8, the rejection of BrO(3) (-) and Br(-) was 68% and 63%, respectively. Donnan exclusion appears to play an important role in determining rejection of BrO(3) (-) and Br(-). In the presence of CaCl(2), rejection of BrO(3) (-) and Br(-) ions was greatly reduced, confirming the importance of electrostatic interactions in determining rejection of BrO(3) (-) and Br(-). The effect of Ca(2+) is so pronounced that in most natural waters, rejection of both BrO(3) (-) and Br(-) by the membrane would be extremely small.

Bromate formation in a hybrid ozonation-ceramic membrane filtration system.

The effect of pH, ozone mass injection rate, initial bromide concentration, and membrane molecular weight cut off (MWCO) on bromate formation in a hybrid membrane filtration-ozonation reactor was studied. Decreasing the pH, significantly reduced bromate formation. Bromate formation increased with increasing gaseous ozone mass injection rate, due to increase in dissolved ozone concentrations. Greater initial bromide concentrations resulted in higher bromate concentrations. An increase in the bromate concentration was observed by reducing MWCO, which resulted in a concomitant increase in the retention time in the system. A model to estimate the rate of bromate formation was developed. Good correlation between the model simulation and the experimental data was achieved.

Single-walled carbon nanotubes dispersed in aqueous media via non-covalent functionalization: effect of dispersant on the stability, cytotoxicity, and epigenetic toxicity of nanotube suspensions.

As the range of applications for carbon nanotubes (CNTs) rapidly expands, understanding the effect of CNTs on prokaryotic and eukaryotic cell systems has become an important research priority, especially in light of recent reports of the facile dispersion of CNTs in a variety of aqueous systems including natural water. In this study, single-walled carbon nanotubes (SWCNTs) were dispersed in water using a range of natural (gum arabic, amylose, Suwannee River natural organic matter) and synthetic (polyvinyl pyrrolidone, Triton X-100) dispersing agents (dispersants) that attach to the CNT surface non-covalently via different physiosorption mechanisms. The charge and the average effective hydrodynamic diameter of suspended SWCNTs as well as the concentration of exfoliated SWCNTs in the dispersion were found to remain relatively stable over a period of 4 weeks. The cytotoxicity of suspended SWCNTs was assessed as a function of dispersant type and exposure time (up to 48 h) using general viability bioassay with Escherichia coli and using neutral red dye uptake (NDU) bioassay with WB-F344 rat liver epithelia cells. In the E. coli viability bioassays, three types of growth media with different organic loadings and salt contents were evaluated. When the dispersant itself was non-toxic, no losses of E. coli and WB-F344 viability were observed. The cell viability was affected only by SWCNTs dispersed using Triton X-100, which was cytotoxic in SWCNT-free (control) solution. The epigenetic toxicity of dispersed CNTs was evaluated using gap junction intercellular communication (GJIC) bioassay applied to WB-F344 rat liver epithelial cells. With all SWCNT suspensions except those where SWCNTs were dispersed using Triton X-100 (wherein GJIC could not be measured because the sample was cytotoxic), no inhibition of GJIC in the presence of SWCNTs was observed. These results suggest a strong dependence of the toxicity of SWCNT suspensions on the toxicity of the dispersant and point to the potential of non-covalent functionalization with non-toxic dispersants as a method for the preparation of stable aqueous suspensions of biocompatible CNTs.

Interactions of aqueous NOM with nanoscale TiO2: implications for ceramic membrane filtration-ozonation hybrid process.

The combined effect of pH and calcium on the interactions of nonozonated and ozonated natural organic matter (NOM) with nanoscale TiO2 was investigated. The approach included characterization of TiO2 nanoparticles and NOM, extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) modeling of NOM-TiO2 and NOM-NOM interactions, batch study on the NOM adsorption onto TiO2 surface, and bench-scale study on the treatment of NOM-containing feed waters using a hybrid process that combines ozonation and ultrafiltration with a 5 kDa ceramic (TiO2 surface) membrane. It was demonstrated that depending on pH and TiO2 loading, the adsorption of NOM species is controlled by either the availability of divalent cations or by preozonation of NOM. XDLVO surface energy analysis predicts NOM adsorption onto TiO2 in the ozone-controlled regime but not in the calcium-controlled regime. In both regimes, short-range NOM-NOM and NOM-TiO2 interactions were governed by acid-base and van der Waals forces, whereas the role of electrostatic forces was relatively insignificant. Ozonation increased the surface energy of NOM, contributing to the hydrophilic repulsion component of the NOM-NOM and NOM-TiO2 interactions. In the calcium-controlled regime, neither NOM-TiO2 nor NOM-NOM interaction controlled adsorption. Non-XDLVO interactions such as intermolecular bridging by calcium were hypothesized to be responsible for the observed adsorption behavior. Adsorption data proved to be highly predictive of the permeate flux performance.

Methylene blue dye test for rapid qualitative detection of hydroxyl radicals formed in a Fenton's reaction aqueous solution.

A new procedure, the methylene blue dye test, qualitatively indicates the presence of hydroxyl radicals through the immediate, distinct bleaching of methylene blue dye on a paper test strip. This method employs a simple procedure requiring inexpensive materials, without the addition of competitive probe chemicals that potentially can interfere with the reaction. A Fenton's reaction with an Fe2+:H2O2 molar ratio of 1:20 generated hydroxyl radicals in Milli-Q water. The presence and absence of hydroxyl radicals were determined prior to and following quenching of the Fenton's reaction with 10% sodium sulfite, respectively. Bleaching of methylene blue dye, due to the presence of hydroxyl radicals in a sample,was indicated by a discoloration from a dark blue color to an almost white color, concentrated at the point of application, with a dark blue outline. A lack of bleaching indicated the absence of hydroxyl radicals in the sample. The presence of hydroxyl radicals was verified by benzoic acid chemical probe experiments with thin-layer chromatography (TLC) and spectrophotometric wavelength scans. The presence of hydroxyl radicals was indirectly determined by detection of hydroxylated benzoic acids on TLC plates and a violet solution color with a peak absorbance at a wavelength close to 520 nm.

Fabrication of catalytic membranes for the treatment of drinking water using combined ozonation and ultrafiltration.

The removal of disinfection byproducts and their precursors was investigated using a combined ozonation-ultrafiltration system. A commercial membrane was coated 20 or 40 times with iron oxide nanoparticles (4-6 nm in diameter). With this membrane, the concentration of dissolved organic carbon was reduced by >85% and the concentrations of simulated distribution system total trihalomethanes and simulated distribution system halo acetic acids decreased by up to 90% and 85%, respectively. When the coated membrane was used, the concentrations of aldehydes, ketones, and ketoacids in the permeate were reduced by >50% as compared to that obtained with the uncoated membranes. Hydroxyl or other radicals produced at the iron oxide coated membrane surface as a result of ozone decomposition are believed to have enhanced the degradation of the natural organic matter, thereby reducing the concentration of disinfection byproducts. While increasing the number of times the membrane was coated from 20 to 40 did not significantly reduce the concentrations of most of the parameters measured, it did result in a significant decrease in the concentrations of ozonation byproducts. Increasing the sintering temperature from 500 to 900 degrees C also resulted in an improvement in the removal of the ozonation byproducts.

Effect of byproducts from the ozonation of pyrene: biphenyl-2,2',6,6'-tetracarbaldehyde and biphenyl-2,2',6,6'-tetracarboxylic acid on gap junction intercellular communication and neutrophil function.

In this study, biphenyl-2,2',6,6'-tetracarbaldehyde, an initial byproduct formed from the ozonation of pyrene, and biphenyl-2,2',6,6'-tetracarboxylic acid, a subsequent pyrene ozonation byproduct, were evaluated using two toxicology assays to compare the toxicity of ozonation byproducts with that of the parent compound. The first assay measured the potential for the compounds to block gap junctional intercellular communication (GJIC) using the scrape loading/dye transfer technique in normal WB-344 rat liver epithelial cells. The second assay evaluated the ability of the compounds to affect neutrophil function by measuring the production of superoxide in a human cell line (HL-60). Pyrene significantly blocked intercellular communication (f = 0.2-0.5) at 40 microM and complete inhibition of communication (f < 0.2) occurred at 50 microM. Gap junctional intercellular communication in cells exposed to biphenyl-2,2',6,6'-tetracarbaldehyde reached f < 0.5 at a concentration of 15 microM. At concentrations greater than 20 microM, biphenyl-2,2',6,6'-tetracarbaldehyde was cytotoxic and the inhibition of GJIC was caused by cell death. Biphenyl-2,2',6,6'-tetracarboxylic acid was neither cytotoxic nor inhibitory to GJIC at the concentrations tested (10-500 microM). Exposure to biphenyl-2,2',6,6'-tetracarbaldehyde resulted in a concentration-dependent decrease in phorbol 12-myristate 13-acetate-stimulated O2- production. Neither exposure to pyrene nor biphenyl-2,2',6,6'-tetracarboxylic acid caused a significant toxic effect on neutrophil function.

Evaluation of biodegradability of NOM after ozonation.

The major purpose of this study was to develop a simple procedure to describe the kinetics of biodegradation of natural organic matter (NOM) in drinking water and to use this procedure to evaluate changes in the concentration of biodegradable organic matter during ozonation and biotreatment. The proposed approach quantitatively describes the formation and removal of rapidly and slowly biodegradable fractions of NOM. This study showed that, depending on source water, ozonation of NOM may result in either minimal formation of biodegradable organic carbon (BDOC), or the formation of predominantly rapidly biodegradable NOM, or in the formation of both rapidly and slowly biodegradable NOM. The kinetic data obtained in this study suggest that while conventional biofiltration processes are capable of removing the rapidly biodegradable fraction, slowly biodegradable organic matter would remain in the filter effluent and may cause bacterial regrowth in the distribution system. An addition of a small amount of easily biodegradable carbon ("stimulated" biodegradation) to ozonated water appears to be effective for the removal of slowly biodegradable organic matter.

Epigenetic toxicity of hydroxylated biphenyls and hydroxylated polychlorinated biphenyls on normal rat liver epithelial cells.

2-Biphenylol, 3-biphenylol, 2,2'-biphenyldiol, 3,3'-biphenyldiol, 3-chloro-2-biphenylol, and 4,4'-dichloro-3-biphenylol were evaluated using the scrape-loading/dye transfer (SL/ DT) technique to determine in vitro gap junctional intercellular communication (GJIC) in a normal rat liver epithelial cell line as a measure of the epigenetic toxicity. Cytotoxicity was determined using the neutral red uptake assay. A dose range of 0-300 microM was examined. Only 3,3'-biphenyldiol and 4,4'-dichloro-3-biphenylol induced cytotoxicity within the tested dose ranges. Noncytotoxic doses were selected for evaluation of epigenetic toxicity. 4,4'-Dichloro-3-biphenylol was most inhibitory to GJIC at the lowest dose. The cytotoxicity and GJIC inhibitory effects observed for 4,4'-dichloro-3-biphenylol might be, although not exclusively, a consequence of the lipophilic nature of this chemical. 3-Chloro-2-biphenylol was least inhibitory to GJIC. 3-Chloro-2-biphenylol was less inhibitory to GJIC than 2-biphenylol because of the presence of the chlorine functional group, which appears to attenuate the toxic effect of the ortho-hydroxyl group. Although cells were capable of complete recovery of GJIC after removal of each of the chemicals, only with 2,2'-biphenyldiol and 4,4,'-dichloro-3-biphenylol did the cells demonstrate partial recovery without removal of the chemical. The more noncoplanar conformation of 2,2'-biphenyldiol and 2-biphenylol might explain their more inhibitory behavior in comparison to 3,3'-biphenyldiol and 3-biphenylol, respectively.

Oxidation kinetics of phenolic and indolic compounds by ozone: applications to synthetic and real swine manure slurry.

In this study, an oxidation model combining the mass transfer of ozone and ozonation kinetics was developed to predict the degradation of several phenolic and indolic compounds in a semi-batch reactor. The mass transfer and partition coefficients were calculated at various physical and chemical conditions. In addition, the reaction rate constants of ozone with phenolic and indolic compounds were also estimated independently using the method of competition kinetics and relative reaction-rate constants. Incorporating mass transfer and chemical reaction concepts, an oxidation model that considers side reactions between ozone and byproducts has been established using non-linear simultaneous differential equations. Thus, numerical computation is capable of simulating the degradation of phenolic and indolic compounds both in synthetic and real manure.