Lynn E. Katz

Reduction of water and energy requirement of algae cultivation using an algae biofilm photobioreactor.

This paper reports the construction and performance of an algae biofilm photobioreactor that offers a significant reduction of the energy and water requirements of cultivation. The green alga Botryococcus braunii was cultivated as a biofilm. The system achieved a direct biomass harvest concentration of 96.4 kg/m(3) with a total lipid content 26.8% by dry weight and a productivity of 0.71 g/m(2) day, representing a light to biomass energy conversion efficiency of 2.02%. Moreover, it reduced the volume of water required to cultivate a kilogram of algal biomass by 45% and reduced the dewatering energy requirement by 99.7% compared to open ponds. Finally, the net energy ratio of the cultivation was 6.00 including dewatering. The current issues of this novel photobioreactor are also identified to further improve the system productivity and scaleup.

Effects of Chloride and Ionic Strength on Physical Morphology, Dissolution, and Bacterial Toxicity of Silver Nanoparticles

In this study, we comprehensively evaluate chloride- and ionic-strength-mediated changes in the physical morphology, dissolution, and bacterial toxicity of silver nanoparticles (AgNPs), which are one of the most-used nanomaterials. The findings isolate the impact of ionic strength from that of chloride concentration. As ionic strength increases, AgNP aggregation likewise increases (such that the hydrodynamic radius [HR] increases), fractal dimension (Df) strongly decreases (providing increased available surface relative to suspensions with higher Df), and the release of Ag(aq) increases. With increased Ag(+) in solution, Escherichia coli demonstrates reduced tolerance to AgNP exposure (i.e., toxicity increases) under higher ionic strength conditions. As chloride concentration increases, aggregates are formed (HR increases) but are dominated by AgCl(0)(s) bridging of AgNPs; relatedly, Df increases. Furthermore, AgNP dissolution strongly increases under increased chloride conditions, but the dominant, theoretical, equilibrium aqueous silver species shift to negatively charged AgClx((x-1)-) species, which appear to be less toxic to E. coli. Thus, E. coli demonstrates increased tolerance to AgNP exposure under higher chloride conditions (i.e., toxicity decreases). Expression measurements of katE, a gene involved in catalase production to alleviate oxidative stress, support oxidative stress in E. coli as a result of Ag(+) exposure. Overall, our work indicates that the environmental impacts of AgNPs must be evaluated under relevant water chemistry conditions.

Measured Effects of Liquid Soil Stabilizers on Engineering Properties of Clay

Stabilization of pavement subgrade soils and base materials has traditionally relied on treatment with lime, cement, and sometimes fly ash. Marketed as alternatives to these conventional bulk soil stabilizers, a variety of concentrated liquid chemical products are sold by several companies. Most transportation agencies, however, are hesitant to specify these nontraditional liquid stabilizers without reliable data to support vendor claims of product effectiveness. Standard laboratory soil tests were conducted to measure changes in the engineering properties of five clay soils when treated with three liquid chemical products. The tests involved three reference clays (kaolinite, illite, montmorillonite), two high-plasticity natural clays, and three representative liquid stabilizers (ionic, polymer, enzyme types). Tests were conducted on untreated control soil samples and on samples treated with each product at the suppliers’ recommended application rates. All of the test specimens were prepared in accordance with a specified 10-step protocol that allowed objective comparisons of the test results. Each treated and untreated soil was characterized in terms of the Atterberg limits, compacted unit weight, one-dimensional free swell potential, and undrained triaxial shear strength. Given some variation in the test samples, the test results did not show consistent, significant changes in the properties of these soils as a result of treatment with these three products. Higher application rates might yield more favorable results. Clearly, independent laboratory evaluations with project-specific soils are warranted before the use of these proprietary liquid stabilizers in the field.

Partitioning of moderately hydrophobic endocrine disruptors between water and synthetic membrane vesicles

The partition coefficient between water and lipid membrane vesicles (Klipw) has been used as an alternative to the 1-octanol-water partition coefficient (Kow) between water and organic solvent, because it more closely represents actual biological membranes. Despite theoretical differences, log Klipw correlates well with log Kow for conventional nonpolar organic pollutants. In the present study, Klipw values of 11 structurally diverse endocrine-disrupting chemicals (EDCs) were measured for three different types of lipid membrane vesicles from dipalmitoylphosphatidylcholine (DPPC), DPPC/cholesterol, and palmitoyloleoylphosphatidylcholine. Correlation analyses were conducted to evaluate the effects of hydrophobicity, molar liquid volume (MLV), and polar surface area (PSA) for 20 EDCs, including nine from a previous study. Correlations that include MLV and PSA reduce the predicted value of log Klipw, suggesting that lipid membranes are less favorable than 1-octanol for a hydrophobic solute because of the higher molar volume and higher hydrogen-bonding potential. These results suggested that Kow alone has limited potential for estimating Klipw and that additional descriptors are required. In addition, Klipw values vary by as much as two orders of magnitude because of the changes in membrane fluidity and the amount of cholesterol in the lipid bilayer. Therefore, lipid components should be chosen carefully to evaluate the bioconcentration of these compounds.

Mechanisms of Soil Stabilization with Liquid Ionic Stabilizer

Numerous commercial suppliers are marketing liquid chemical products for stabilizing pavement subgrade and base soils. These nontraditional chemical stabilizers may offer viable alternatives for stabilizing sulfate-rich soils where conventional lime or cement treatment can lead to excessive soil expansion. Typically sold as concentrated liquids that are diluted in water before application, these products may be less expensive to use than lime or cement. However, many transportation agencies are hesitant to specify nontraditional liquid stabilizers without better information on the stabilizing mechanisms and documented field experiences. To identify the mechanisms associated with one class of these products, a representative ionic soil stabilizer and a sodium montmorillonite clay were selected for a detailed physical-chemical study. Laboratory testing included chromatography, spectroscopy, X-ray diffraction, electron microscopy, and standard titration analyses. These tests have shown that the principal active constituents of the selected ionic stabilizer are d-limonene (a by-product of citrus processing) and sulfuric acid, which react to form a concentrated, low-pH solution of sulfonated limonene. The observed changes in clay chemistry following treatment indicated that this product would stabilize a soil by altering the clay lattice. The result is the formation of a more highly weathered, less-expansive clay structure. On the basis of this understanding of the underlying mechanisms, ionic stabilizers applied at sufficiently high application mass ratios may improve the properties of certain soils on some highway construction projects.

Cometabolism of trihalomethanes by Nitrosomonas europaea.

ABSTRACT The ammonia-oxidizing bacterium Nitrosomonas europaea (ATCC 19718) was shown to degrade low concentrations (50 to 800 μg/liter) of the four trihalomethanes (trichloromethane [TCM], or chloroform; bromodichloromethane [BDCM]; dibromochloromethane [DBCM]; and tribromomethane [TBM], or bromoform) commonly found in treated drinking water. Individual trihalomethane (THM) rate constants (\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(k_{1_{THM}}\) \end{document}) increased with increasing THM bromine substitution, with TBM > DBCM > BDCM > TCM (0.23, 0.20, 0.15, and 0.10 liters/mg/day, respectively). Degradation kinetics were best described by a reductant model that accounted for two limiting reactants, THMs and ammonia-nitrogen (NH3-N). A decrease in the temperature resulted in a decrease in both ammonia and THM degradation rates with ammonia rates affected to a greater extent than THM degradation rates. Similarly to the THM degradation rates, product toxicity, measured by transformation capacity (Tc), increased with increasing THM bromine substitution. Because both the rate constants and product toxicities increase with increasing THM bromine substitution, a waters THM speciation will be an important consideration for process implementation during drinking water treatment. Even though a given water sample may be kinetically favored based on THM speciation, the resulting THM product toxicity may not allow stable treatment process performance.

Gas-phase formaldehyde adsorption isotherm studies on activated carbon: Correlations of adsorption capacity to surface functional group density

Formaldehyde (HCHO) adsorption isotherms were developed for the first time on three activated carbons representing one activated carbon fiber (ACF) cloth, one all-purpose granular activated carbon (GAC), and one GAC commercially promoted for gas-phase HCHO removal. The three activated carbons were evaluated for HCHO removal in the low-ppm(v) range and for water vapor adsorption from relative pressures of 0.1-0.9 at 26 °C where, according to the IUPAC isotherm classification system, the adsorption isotherms observed exhibited Type V behavior. A Type V adsorption isotherm model recently proposed by Qi and LeVan (Q-L) was selected to model the observed adsorption behavior because it reduces to a finite, nonzero limit at low partial pressures and it describes the entire range of adsorption considered in this study. The Q-L model was applied to a polar organic adsorbate to fit HCHO adsorption isotherms for the three activated carbons. The physical and chemical characteristics of the activated carbon surfaces were characterized using nitrogen adsorption isotherms, X-ray photoelectron spectroscopy (XPS), and Boehm titrations. At low concentrations, HCHO adsorption capacity was most strongly related to the density of basic surface functional groups (SFGs), while water vapor adsorption was most strongly influenced by the density of acidic SFGs.

Use of a parallel artificial membrane system to evaluate passive absorption and elimination in small fish

A parallel artificial lipid membrane system was developed to mimic passive mass transfer of hydrophobic organic chemicals in fish. In this physical model system, a membrane filter-supported lipid bilayer separates two aqueous phases that represent the external and internal aqueous environments of fish. To predict bioconcentration kinetics in small fish with this system, literature absorption and elimination rates were analyzed with an allometric diffusion model to quantify the mass transfer resistances in the aqueous and lipid phases of fish. The effect of the aqueous phase mass transfer resistance was controlled by adjusting stirring intensity to mimic bioconcentration rates in small fish. Twenty-three simple aromatic hydrocarbons were chosen as model compounds for purposes of evaluation. For most of the selected chemicals, literature absorption/elimination rates fall into the range predicted from measured membrane permeabilities and elimination rates of the selected chemicals determined by the diffusion model system.

Biogeochemical Changes and Mercury Methylation beneath an In-Situ Sediment Cap†

In-situ capping has shown promise as a management strategy for contaminated aquatic sediments, however, little is known about how mercury methylation in underlying sediments will be affected. Changes to the location and extent of sulfate reduction and other biological processes were studied in estuarine sediment using laboratory microcosms. Observations in a model sediment showed increases of in situ total methylmercury concomitant with an upward extension of anaerobic bacterial activity beneath a sediment cap and under anoxic conditions. Increased methylmercury (up to 50%) was observed beneath a sediment cap in a region 2-3 cm higher than in an uncapped sediment. A 1-dimensional, unsteady, reaction transport model was used to simulate the transient response to mercury-related biogeochemical processes. The location, magnitude, and expected duration of the increased methylmercury was such that a significant impact on near cap-water interface methylmercury was not expected for the sediments studied. Explicit consideration of the biogeochemical effects of capping on mercury contaminated sediment, however, may be necessary for very thin or unstable capping layers where the physical sequestration provided by a cap may be compromised.

Performance and biofilm activity of nitrifying biofilters removing trihalomethanes.

Nitrifying biofilters seeded with three different mixed-culture sources removed trichloromethane (TCM) and dibromochloromethane (DBCM) with removals reaching 18% for TCM and 75% for DBCM. In addition, resuspended biofilm removed TCM, bromodichloromethane (BDCM), DBCM, and tribromomethane (TBM) in backwash batch kinetic tests, demonstrating that the biofilters contained organisms capable of biotransforming the four regulated trihalomethanes (THMs) commonly found in treated drinking water. Upon the initial and subsequent increased TCM addition, total ammonia nitrogen (TOTNH(3)) removal decreased and then reestablished, indicating an adjustment by the biofilm bacteria. In addition, changes in DBCM removal indicated a change in activity related to DBCM. The backwash batch kinetic tests provided a useful tool to evaluate the biofilms bacteria. Based on these experiments, the biofilters contained bacteria with similar THM removal kinetics to those seen in previous batch kinetic experiments. Overall, performance or selection does not seem based specifically on nutrients, source water, or source cultures and most likely results from THM product toxicity, and the use of GAC media appeared to offer benefits over anthracite for biofilter stability and long-term performance, although the reasons for this advantage are not apparent based on research to date.