Akram N. Alshawabkeh

Distribution, Variability, and Predictors of Urinary Concentrations of Phenols and Parabens among Pregnant Women in Puerto Rico

Puerto Rico has higher rates of a range of endocrine-related diseases and disorders compared to the United States. However, little is known to date about human exposures to known or potential endocrine disrupting chemicals (EDCs) in Puerto Rico. We recruited 105 pregnant women in Northern Puerto Rico who provided urine samples and questionnaire data at three times (18 ± 2, 22 ± 2, and 26 ± 2 weeks) during gestation. We measured the urinary concentrations of five phenols and three parabens: 2,4-dichlorophenol (24-DCP), 2,5-dichlorophenol (25-DCP), benzophenone-3 (BP-3), bisphenol A (BPA), triclosan (TCS), butyl paraben (B-PB), methyl paraben (M-PB), and propyl paraben (P-PB). The frequent detection of these chemicals suggests that exposure is highly prevalent among these Puerto Rican pregnant women. Urinary concentrations of TCS, BP-3, and 25-DCP were higher than among women of reproductive age in the US general population, while concentrations of BPA, 24-DCP, and parabens were similar. Intraclass correlation coefficients (ICC) varied widely between biomarkers; BPA had the lowest ICC (0.24) and BP-3 had the highest (0.62), followed by 25-DCP (0.49) and TCS (0.47). We found positive associations between biomarker concentrations with self-reported use of liquid soap (TCS), sunscreen (BP-3), lotion (BP-3 and parabens), and cosmetics (parabens). Our results can inform future epidemiology studies and strategies to reduce exposure to these chemicals or their precursors.

ENHANCED ELECTROKINETIC REMEDIATION OF HIGH SORPTION CAPACITY SOIL

Abstract In unenhanced electrokinetic remediation of metals, electrolysis reactions at the cathode generate a high pH medium that results in metal precipitation and immobilization in the soil. Different enhancement procedures could be utilized at the electrodes to prevent or hinder the generation and transport of this alkaline medium into the soil. This study investigates the feasibility of enhanced extraction of metals from high sorption capacity soils by the use of acetic acid to neutralize the cathode electrolysis reaction and also the use of an ion selective (Nafion TM ) membrane to prevent back-transport of the OH − generated at the cathode. Synthetic soil samples spiked with lead were used in the testing. Synthetic soils were a mixture of 40% illite, 8% kaolinite, 5% Na-montmorillonite and 47% fine sand representing an illitic deposit. The results demonstrate the feasibility of extracting lead from the deposit. Acetic acid and Nafion enhancement resulted in better removal efficiencies and lead electrodepositions at the cathode compared to unenhanced tests. However, higher energy expenditure and longer processing periods were required when compared to enhanced extraction of lead from kaolinite. Acetic acid tests required less energy than membrane tests.

Electrolytic Manipulation of Persulfate Reactivity by Iron Electrodes for Trichloroethylene Degradation in Groundwater

Activated persulfate oxidation is an effective in situ chemical oxidation process for groundwater remediation. However, reactivity of persulfate is difficult to manipulate or control in the subsurface causing activation before reaching the contaminated zone and leading to a loss of chemicals. Furthermore, mobilization of heavy metals by the process is a potential risk. An effective approach using iron electrodes is thus developed to manipulate the reactivity of persulfate in situ for trichloroethylene (TCE) degradation in groundwater and to limit heavy metals mobilization. TCE degradation is quantitatively accelerated or inhibited by adjusting the current applied to the iron electrode, following k1 = 0.00053·Iv + 0.059 (-122 A/m(3) ≤ Iv ≤ 244 A/m(3)) where k1 and Iv are the pseudo first-order rate constant (min(-1)) and volume normalized current (A/m(3)), respectively. Persulfate is mainly decomposed by Fe(2+) produced from the electrochemical and chemical corrosion of iron followed by the regeneration via Fe(3+) reduction on the cathode. SO4(•-) and ·OH cocontribute to TCE degradation, but ·OH contribution is more significant. Groundwater pH and oxidation-reduction potential can be restored to natural levels by the continuation of electrolysis after the disappearance of contaminants and persulfate, thus decreasing adverse impacts such as the mobility of heavy metals in the subsurface.

Urinary phthalate metabolite concentrations among pregnant women in Northern Puerto Rico: Distribution, temporal variability, and predictors

BACKGROUND Phthalate contamination exists in the North Coast karst aquifer system in Puerto Rico. In light of potential health impacts associated with phthalate exposure, targeted action for elimination of exposure sources may be warranted, especially for sensitive populations such as pregnant women. However, information on exposure to phthalates from a variety of sources in Puerto Rico is lacking. The objective of this study was to determine concentrations and predictors of urinary phthalate biomarkers measured at multiple times during pregnancy among women living in the Northern karst area of Puerto Rico. METHODS We recruited 139 pregnant women in Northern Puerto Rico and collected urine samples and questionnaire data at three separate visits (18 ± 2 weeks, 22 ± 2 weeks, and 26 ± 2 weeks of gestation). Urine samples were analyzed for eleven phthalate metabolites: mono-2-ethylhexyl phthalate (MEHP), mono-2-ethyl-5-hydroxyhexyl phthalate, mono-2-ethyl-5-oxohexyl phthalate, mono-2-ethyl-5-carboxypentyl phthalate, mono-ethyl phthalate (MEP), mono-n-butyl phthalate, mono-benzyl phthalate, mono-isobutyl phthalate, mono-3-carboxypropyl phthalate (MCPP), mono carboxyisononyl phthalate (MCNP), and mono carboxyisooctyl phthalate (MCOP). RESULTS Detectable concentrations of phthalate metabolites among pregnant women living in Puerto Rico was prevalent, and metabolite concentrations tended to be higher than or similar to those measured in women of reproductive age from the general US population. Intraclass correlation coefficients ranged from very weak (MCNP; 0.05) to moderate (MEP; 0.44) reproducibility among all phthalate metabolites. We observed significant or suggestive positive associations between urinary phthalate metabolite concentrations and water usage/storage habits (MEP, MCNP, MCOP), use of personal care products (MEP), and consumption of certain food items (MCPP, MCNP, and MCOP). CONCLUSIONS To our knowledge this is the first study to report concentrations, temporal variability, and predictors of phthalate biomarkers among pregnant women in Puerto Rico. Preliminary results suggest several potentially important exposure sources to phthalates in this population and future analysis from this ongoing prospective cohort will help to inform targeted approaches to reduce exposure.

Coupling of electrochemical and mechanical processes in soils under DC fields

Abstract Direct current (DC) electric fields have been applied in several geotechnical and geoenvironmental engineering applications, including electro-osmotic dewatering and consolidation, ion injection and contaminant removal. Such applications cause electrochemical effects in the soil, leading to changes in the soil’s physical, chemical and mechanical properties. Some of these changes have been evaluated extensively (such as those occurring under electro-osmotic consolidation) based on the assumption that electrochemical conditions are uniform between the electrodes. However, recent studies have shown that nonlinearity in these conditions develop between the electrodes leading to changes in the chemical, physical and mechanical properties of the soil. This paper evaluates the nonlinear effects on these properties as measured in some specific applications. In particular, the application of DC fields to soft soils is shown to alter the soil in both its mechanical and physical properties. The soil’s undrained shear strength is increased by interparticle cementation brought about by the electrochemical injection of ions into the soil under the DC field. In addition, soils can consolidate or swell under these fields. In both of these cases, the development of a nonlinear voltage distribution across the soil is clearly measured, and can affect the progression of any electrochemical soil treatment as well as the accuracy with which it is modeled.

Electrokinetic Soil Remediation: Challenges and Opportunities

Abstract Electrokinetic remediation is effective for extraction of contaminants, such as heavy metals, from fine grained deposits. However, several challenges have led to limited field implementation in the US over the past two decades. The reasons include lower risk of exposure to adsorbed contaminants through groundwater, cost of treatment, technical challenges in difficult soil, and complex geochemical conditions, and the need for acidification to induce desorption. To address practical implementation, a Reactive Transference Factor can be used to identify conditions that are favorable for electrokinetic remediation. The factor measures the reactive transport rates relative to the electrical conductivity of the soil. Other opportunities are identified for implementation of electric-based methods for remediation beyond heavy metal extraction. These include enhancement of bioremediation, which is favorable for remediation of hot spots or source areas, and the development of reactive electrochemical barriers, particularly for the treatment of contaminated groundwater plumes.

Efficient degradation of TCE in groundwater using Pd and electro-generated H2 and O2: a shift in pathway from hydrodechlorination to oxidation in the presence of ferrous ions.

Degradation of trichloroethylene (TCE) in simulated groundwater by Pd and electro-generated H(2) and O(2) is investigated in the absence and presence of Fe(II). In the absence of Fe(II), hydrodechlorination dominates TCE degradation, with accumulation of H(2)O(2) up to 17 mg/L. Under weak acidity, low concentrations of oxidizing •OH radicals are detected due to decomposition of H(2)O(2), slightly contributing to TCE degradation via oxidation. In the presence of Fe(II), the degradation efficiency of TCE at 396 μM improves to 94.9% within 80 min. The product distribution proves that the degradation pathway shifts from 79% hydrodechlorination in the absence of Fe(II) to 84% •OH oxidation in the presence of Fe(II). TCE degradation follows zeroth-order kinetics with rate constants increasing from 2.0 to 4.6 μM/min with increasing initial Fe(II) concentration from 0 to 27.3 mg/L at pH 4. A good correlation between TCE degradation rate constants and •OH generation rate constants confirms that •OH is the predominant reactive species for TCE oxidation. Presence of 10 mM Na(2)SO(4), NaCl, NaNO(3), NaHCO(3), K(2)SO(4), CaSO(4), and MgSO(4) does not significantly influence degradation, but sulfite and sulfide greatly enhance and slightly suppress degradation, respectively. A novel Pd-based electrochemical process is proposed for groundwater remediation.

Optimization of 2-D Electrode Configuration for Electrokinetic Remediation

A practical evaluation of one- and two-dimensional applications of electric fields for in situ extraction of contaminants is provided. The evaluation is based on contaminant transport by electroosmosis and ion migration. Parameters evaluated include electrode requirements, effectiveness of electric field distribution, remediation time, and energy expenditure. Formulation is provided for calculating cost components of the process, including electrode, energy, chemicals, posttreatment, fixed, and variable costs. Equations are also provided for evaluating optimum electrode spacings based on energy and time requirements. The derivations show that spacing between same-polarity electrodes is as significant in cost calculations and in process effectiveness as that between anodes and cathodes. Decreasing the same-polarity electrode spacing to half the anode-cathode spacing will result in a 100% increase in electrode requirements, but will decrease the area of the ineffective electric field by one half. Selection ...

Associations between urinary phenol and paraben concentrations and markers of oxidative stress and inflammation among pregnant women in Puerto Rico.

Phenols and parabens are used in a multitude of consumer products resulting in ubiquitous human exposure. Animal and in vitro studies suggest that exposure to these compounds may be related to a number of adverse health outcomes, as well as potential mediators such as oxidative stress and inflammation. We examined urinary phenol (bisphenol A (BPA), triclosan (TCS), benzophenone-3 (BP-3), 2,4-dichlorophenol (24-DCP), 2,5-dichlorophenol (25-DCP)) and paraben (butyl paraben (B-PB), methyl paraben (M-PB), propyl paraben (P-PB)) concentrations measured three times during pregnancy in relation to markers of oxidative stress and inflammation among participants in the Puerto Rico Testsite for Exploring Contamination Threats (PROTECT) project. Serum markers of inflammation (c-reactive protein (CRP), IL-1β, IL-6, IL-10, and tumor necrosis factor-α (TNF-α)) were measured twice during pregnancy (n=105 subjects, 187 measurements) and urinary markers of oxidative stress (8-hydroxydeoxyguanosine (OHdG) and isoprostane) were measured three times during pregnancy (n=54 subjects, 146 measurements). We used linear mixed models to assess relationships between natural log-transformed exposure and outcome biomarkers while accounting for within individual correlation across study visits. After adjustment for urinary specific gravity, study visit, maternal pre-pregnancy BMI, and maternal education, an interquartile range (IQR) increase in urinary BPA was associated with 21% higher OHdG (p=0.001) and 29% higher isoprostane (p=0.0002), indicating increased oxidative stress. The adjusted increase in isoprostane per IQR increase in marker of exposure was 17% for BP-3, 27% for B-PB, and 20% for P-PB (all p<0.05). An IQR increase in triclosan (TCS) was associated with 31% higher serum concentrations of IL-6 (p=0.007), a pro-inflammatory cytokine. In contrast, IQR increases in BP-3 and B-PB were significantly associated with 16% and 18% lower CRP, a measure of systemic inflammation. Our findings suggest that exposure to BPA, select parabens, and TCS during pregnancy may be related to oxidative stress and inflammation, potential mechanisms by which exposure to these compounds may influence birth outcomes and other adverse health effects, but additional research is needed.

Redox control for electrochemical dechlorination of trichloroethylene in bicarbonate aqueous media

The role of iron anode on electrochemical dechlorination of aqueous trichloroethylene (TCE) is evaluated using batch mixed-electrolyte experiments. A significantly higher dechlorination rate, up to 99%, is reported when iron anode and copper foam cathodes are used. In contrast to the oxygen-releasing inert anode, the cast iron anode generates ferrous species, which regulate the electrolyte to a reducing condition (low ORP value) and favor the reduction of TCE. The main products of TCE electrochemical reduction on copper foam cathode include ethene and ethane. The ratio of these two hydrocarbons gases varied with the electrolyte ORP condition and current density as more ethane gas generates at more reducing electrolyte condition and at higher current condition. A pseudofirst-order model is used to describe the degradation of TCE; the first-order rate constant (k) increases with the current applied but exhibits a negative relation with initial concentration. Depending on the current, electrolysis by iron anode causes a reduction in the ORP and an increase in the pH of the mixed electrolyte. Enhanced reaction rates in this investigation indicate that the electrochemical reduction using copper foam and iron anode may be a promising process for remediation of groundwater contaminated with chlorinated organic compounds.