Showing papers in "Environmental Science & Technology in 2004"

Radical generation by the interaction of transition metals with common oxidants.

Abstract: Nine transition metals were tested for the activation of three oxidants and the generation of inorganic radical species such as sulfate, peroxymonosulfate, and hydroxyl radicals. From the 27 combinations, 14 M/Ox couples demonstrated significant reactivity toward transforming a model organic substrate such as 2,4-dichlorophenol and are further discussed here. It was found that Co(II) and Ru(III) are the best metal catalysts for the activation of peroxymonosulfate. As expected on the basis of the Fenton reagent, Fe(III) and Fe(II) were the most efficient transition metals for the activation of hydrogen peroxide. Finally, Ag(I) showed the best results toward activating persulfate. Quenching studies with specific alcohols (tert-butyl alcohol and ethanol) were also performed to identify the primary radical species formed from the reactive M/Ox interactions. The determination of these transient species allowed us to postulate the rate-determining step of the redox reactions taking place when a metal is coupled with an oxidant in aqueous solution. It was found that when Co(II), Ru(III), and Fe(II) interact with peroxymonosulfate, freely diffusible sulfate radicals are the primary species formed. The same was proven for the interaction of Ag(I) with persulfate, but in this case caged or bound to the metal sulfate radicals might be formed as well. The conjunction of Ce(III), Mn(II), and Ni(II) with peroxymonosulfate showed also to generate caged or bound to the metal sulfate radicals. A combination of sulfate and hydroxyl radicals was formed from the conjunction of V(III) with peroxymonosulfate and from Fe(II) with persulfate. Finally, the conjunction of Fe(III), Fe(II), and Ru(III) with hydrogen peroxide led primarily to the generation of hydroxyl radicals. It is also suggested here that the redox behavior of a particular metal in solution cannot be predicted based exclusively on its size and charge. Additional phenomena such as metal hydrolysis as well as complexation with other counterions present in solution might affect the thermodynamics of the overall process and are further discussed here.

Electricity generation using an air-cathode single chamber microbial fuel cell in the presence and absence of a proton exchange membrane.

Abstract: Microbial fuel cells (MFCs) are typically designed as a two-chamber system with the bacteria in the anode chamber separated from the cathode chamber by a polymeric proton exchange membrane (PEM). Most MFCs use aqueous cathodes where water is bubbled with air to provide dissolved oxygen to electrode. To increase energy output and reduce the cost of MFCs, we examined power generation in an air-cathode MFC containing carbon electrodes in the presence and absence of a polymeric proton exchange membrane (PEM). Bacteria present in domestic wastewater were used as the biocatalyst, and glucose and wastewater were tested as substrates. Power density was found to be much greater than typically reported for aqueous-cathode MFCs, reaching a maximum of 262 ± 10 mW/m2 (6.6 ± 0.3 mW/L; liquid volume) using glucose. Removing the PEM increased the maximum power density to 494 ± 21 mW/m2 (12.5 ± 0.5 mW/L). Coulombic efficiency was 40−55% with the PEM and 9−12% with the PEM removed, indicating substantial oxygen diffusion i...

Polybrominated Diphenyl Ethers in the Environment and in People: A Meta-Analysis of Concentrations

Abstract: Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in many types of consumer products. Perhaps as a result of their widespread use and their lipophilicity, these compounds have become ubiquitous in the environment and in people. This review summarizes PBDE concentrations measured in several environmental media and analyzes these data in terms of relative concentrations, concentration trends, and congener profiles. In human blood, milk, and tissues, total PBDE levels have increased exponentially by a factor of ∼100 during the last 30 yr; this is a doubling time of ∼5 yr. The current PBDE concentrations in people from Europe are ∼2 ng/g lipid, but the concentrations in people from the United States are much higher at ∼35 ng/g lipid. Current PBDE concentrations in marine mammals from the Canadian Arctic are very low at ∼5 ng/g lipid, but they have increased exponentially with a doubling time of ∼7 yr. Marine mammals from the rest of the world have current PBDE levels of ∼1000 ng/g lipid, and...

Production of electricity during wastewater treatment using a single chamber microbial fuel cell.

Abstract: Microbial fuel cells (MFCs) have been used to produce electricity from different compounds, including acetate, lactate, and glucose. We demonstrate here that it is also possible to produce electricity in a MFC from domestic wastewater, while atthe same time accomplishing biological wastewater treatment (removal of chemical oxygen demand; COD). Tests were conducted using a single chamber microbial fuel cell (SCMFC) containing eight graphite electrodes (anodes) and a single air cathode. The system was operated under continuous flow conditions with primary clarifier effluent obtained from a local wastewater treatment plant. The prototype SCMFC reactor generated electrical power (maximum of 26 mW m(-2)) while removing up to 80% of the COD of the wastewater. Power output was proportional to the hydraulic retention time over a range of 3-33 h and to the influent wastewater strength over a range of 50-220 mg/L of COD. Current generation was controlled primarily by the efficiency of the cathode. Optimal cathode performance was obtained by allowing passive air flow rather than forced air flow (4.5-5.5 L/min). The Coulombic efficiency of the system, based on COD removal and current generation, was < 12% indicating a substantial fraction of the organic matter was lost without current generation. Bioreactors based on power generation in MFCs may represent a completely new approach to wastewater treatment. If power generation in these systems can be increased, MFC technology may provide a new method to offset wastewater treatment plant operating costs, making advanced wastewater treatment more affordable for both developing and industrialized nations.

Correlation equation for predicting single-collector efficiency in physicochemical filtration in saturated porous media.

Abstract: A new equation for predicting the single-collector contact efficiency (eta0) in physicochemical particle filtration in saturated porous media is presented. The correlation equation is developed assuming that the overall single-collector efficiency can be calculated as the sum of the contributions of the individual transport mechanisms--Brownian diffusion, interception, and gravitational sedimentation. To obtain the correlation equation, the dimensionless parameters governing particle deposition are regressed against the theoretical value of the single-collector efficiency over a broad range of parameter values. Rigorous numerical solution of the convective-diffusion equation with hydrodynamic interactions and universal van der Waals attractive forces fully incorporated provided the theoretical single-collector efficiencies. The resulting equation overcomes the limitations of current approaches and shows remarkable agreement with exact theoretical predictions of the single-collector efficiency over a wide range of conditions commonly encountered in natural and engineered aquatic systems. Furthermore, experimental data are in much closer agreement with predictions based on the new correlation equation compared to other available expressions.

Perfluorooctanesulfonate and related fluorochemicals in human blood from several countries.

Abstract: Perfluorooctanesulfonyl fluoride based compounds have been used in a wide variety of consumer products, such as carpets, upholstery, and textiles. These compounds degrade to perfluorooctanesulfonat...

System Boundary Selection in Life-Cycle Inventories Using Hybrid Approaches

Abstract: Life-cycle assessment (LCA) is a method for evaluating the environmental impacts of products holistically, including direct and supply chain impacts. The current LCA methodologies and the standards by the International Organization for Standardization (ISO) impose practical difficulties for drawing system boundaries; decisions on inclusion or exclusion of processes in an analysis (the cutoff criteria) are typically not made on a scientific basis. In particular, the requirement of deciding which processes could be excluded from the inventory can be rather difficult to meet because many excluded processes have often never been assessed by the practitioner, and therefore, their negligibility cannot be guaranteed. LCA studies utilizing economic input-output analysis have shown that, in practice, excluded processes can contribute as much to the product system under study as included processes; thus, the subjective determination of the system boundary may lead to invalid results. System boundaries in LCA are discussed herein with particular attention to outlining hybrid approaches as methods for resolving the boundary selection problem in LCA. An input-output model can be used to describe at least a part of a product system, and an ISO-compatible system boundary selection procedure can be designed by applying hybrid input-output-assisted approaches. There are several hybrid input-output analysis-based LCA methods that can be implemented in practice for broadening system boundary and also for ISO compliance.

Compositions and sorptive properties of crop residue-derived chars.

Abstract: Chars originating from the burning or pyrolysis of vegetation may significantly sorb neutral organic contaminants (NOCs). To evaluate the relationship between the char composition and NOC sorption,...

Degradation of fluorotelomer alcohols: a likely atmospheric source of perfluorinated carboxylic acids.

Abstract: Human and animal tissues collected in urban and remote global locations contain persistent and bioaccumulative perfluorinated carboxylic acids (PFCAs). The source of PFCAs was previously unknown. Here we present smog chamber studies that indicate fluorotelomer alcohols (FTOHs) can degrade in the atmosphere to yield a homologous series of PFCAs. Atmospheric degradation of FTOHs is likely to contribute to the widespread dissemination of PFCAs. After their bioaccumulation potential is accounted for, the pattern of PFCAs yielded from FTOHs could account for the distinct contamination profile of PFCAs observed in arctic animals. Furthermore, polar bear liver was shown to contain predominately linear isomers (>99%) of perfluorononanoic acid (PFNA), while both branched and linear isomers were observed for perfluorooctanoic acid, strongly suggesting a sole input of PFNA from “telomer”-based products. The significance of the gas-phase peroxy radical cross reactions that produce PFCAs has not been recognized previo...

Continuous electricity generation from domestic wastewater and organic substrates in a flat plate microbial fuel cell.

Abstract: A microbial fuel cell (MFC) is a device that converts organic matter to electricity using microorganisms as the biocatalyst. Most MFCs contain two electrodes separated into one or two chambers that are operated as a completely mixed reactor. In this study, a flat plate MFC (FPMFC) was designed to operate as a plug flow reactor (no mixing) using a combined electrode/proton exchange membrane (PEM) system. The reactor consisted of a single channel formed between two nonconductive plates that were separated into two halves by the electrode/PEM assembly. Each electrode was placed on an opposite side of the PEM, with the anode facing the chamber containing the liquid phase and the cathode facing a chamber containing only air. Electricity generation using the FPMFC was examined by continuously feeding a solution containing wastewater, or a specific substrate, into the anode chamber. The system was initially acclimated for 1 month using domestic wastewater orwastewater enriched with a specific substrate such as acetate. Average power density using only domestic wastewater was 72+/-1 mW/m2 at a liquid flow rate of 0.39 mL/min [42% COD (chemical oxygen demand) removal, 1.1 h HRT (hydraulic retention time)]. At a longer HRT = 4.0 h, there was 79% COD removal and an average power density of 43+/-1 mW/m2. Power output was found to be a function of wastewater strength according to a Monod-type relationship, with a half-saturation constant of Ks = 461 or 719 mg COD/L. Power generation was sustained at high rates with several organic substrates (all at approximately 1000 mg COD/L), including glucose (212+/-2 mW/ m2), acetate (286+/-3 mW/m2), butyrate (220+/-1 mW/ m2), dextran (150+/-1 mW/m2), and starch (242+/-3 mW/ m2). These results demonstrate the versatility of power generation in a MFC with a variety of organic substrates and show that power can be generated at a high rate in a continuous flow reactor system.

Occurrence of antimicrobials in the final effluents of wastewater treatment plants in Canada.

Abstract: To investigate the occurrence of antimicrobials in the final effluents from wastewater treatment plants (WWTPs) in Canada, analytical methods were developed or modified from previously described methods using solid-phase extraction followed by liquid chromatography−electrospray ionization tandem mass spectrometry. Thirty-one antimicrobials from the macrolide, quinolone, quinoxaline dioxide, sulfonamide, and tetracycline classes were investigated in the final (treated) effluents from eight WWTPs, located in five Canadian cities. Ciprofloxacin, clarithromycin, erythromycin-H2O, ofloxacin, sulfamethoxazole, sulfapyridine, and tetracycline were frequently detected in the effluents. The detection of sulfapyridine in effluents is the first report of this compound in environmental samples. Antimicrobials used exclusively for veterinary applications or treatment of livestock, such as carbadox, olaquindox, and chlortetracycline were not detected in the WWTP final effluents. There appear to be differences in the re...

Organic Fouling and Chemical Cleaning of Nanofiltration Membranes: Measurements and Mechanisms

Abstract: Fouling and subsequent chemical cleaning of nanofiltration (NF) membranes used in water quality control applications are often inevitable. To unravel the mechanisms of organic fouling and chemical cleaning, it is critical to understand the foulant-membrane, foulant-foulant, and foulant-cleaning agent interactions at the molecular level. In this study, the adhesion forces between the foulant and the membrane surface and between the bulk foulant and the fouling layer were determined by atomic force microscopy (AFM). A carboxylate modified AFM colloid probe was used as a surrogate for humic acid, the major organic foulant in natural waters. The interfacial force data were combined with the NF membrane water flux measurements to elucidate the mechanisms of organic fouling and chemical cleaning. A remarkable correlation was obtained between the measured adhesion forces and the fouling and cleaning behavior of the membrane under various solution chemistries. The AFM measurements further confirmed that divalent calcium ions greatly enhance natural organic matter fouling by complexation and subsequent formation of intermolecular bridges among organic foulant molecules. Efficient chemical cleaning was achieved only when the calcium ion bridging was eliminated as a result of the interaction between the chemical cleaning agent and the fouling layer. The cleaning efficiency was highly dependent on solution pH and the concentration of the chemical cleaning agent.

Identification of Long-Chain Perfluorinated Acids in Biota from the Canadian Arctic

Abstract: Recently it was discovered that humans and animals from various urban and remote global locations contained a novel class of persistent fluorinated contaminants, the most pervasive of which was perfluorooctane sulfonate (PFOS). Lower concentrations of perfluorooctanoate, perfluorohexane sulfonate, and heptadecafluorooctane sulfonamide have also been detected in various samples. Although longer perfluoroalkyl carboxylates (PFCAs) are used in industry and have been detected in fish following a spill of aqueous film forming foam, no studies have been conducted to examine the widespread occurrence of long-chain PFCAs (e.g., CF3(CF2)xCOO-, where x > 6). To provide a preliminary assessment of fluorinated contaminants, including PFCAs, in the Canadian Arctic, polar bears, ringed seals, arctic fox, mink, common loons, northern fulmars, black guillemots, and fish were collected at various locations in the circumpolar region. PFOS was the major contaminant detected in most samples and in polar bear liver was the most prominent organohalogen (mean PFOS = 3.1 microg/g wet weight) compared to individual polychlorinated biphenyl congeners, chlordane, or hexachlorocyclohexane-related chemicals in fat. Using two independent mass spectral techniques, it was confirmed that all samples also contained ng/g concentrations of a homologous series of PFCAs, ranging in length from 9 to 15 carbons. Sum concentrations of PFCAs (sum(PFCAs)) were lower than total PFOS equivalents (sum(PFOS)) in all samples except for mink. In mink, perfluorononanoate (PFNA) concentrations exceeded PFOS concentrations, indicating that PFNA and other PFCAs should be considered in future risk assessments. Mammals feeding at higher trophic levels had greater concentrations of PFOS and PFCAs than mammals feeding at lower trophic positions. In general, odd-length PFCAs exceeded the concentration of even-length PFCAs, and concentrations decreased with increasing chain length in mammals. PFOS and PFCA concentrations were much lower for animals living in the Canadian Arctic than for the same species living in mid-latitude regions of the United States. Future studies should continue to monitor all fluorinated contaminants and examine the absolute and relative toxicities for this novel suite of PFCAs.

Biotic Ligand Model, a Flexible Tool for Developing Site-Specific Water Quality Guidelines for Metals

Abstract: The biotic ligand model (BLM) is a mechanistic approach that greatly improves our ability to generate site-specific ambient water quality criteria (AWQC)for metals in the natural environment relative to conventional relationships based only on hardness. The model is flexible; all aspects of water chemistry that affect toxicity can be included, so the BLM integrates the concept of bioavailability into AWQC--in essence the computational equivalent of water effect ratio (WER) testing. The theory of the BLM evolved from the gill surface interaction model (GSIM) and the free ion activity model (FIAM). Using an equilibrium geochemical modeling framework, the BLM incorporates the competition of the free metal ion with other naturally occurring cations (e.g., Ca2+, Na+, Mg2-, H+), togetherwith complexation by abiotic ligands [e.g., DOM (dissolved organic matter), chloride, carbonates, sulfide] for binding with the biotic ligand, the site of toxic action on the organism. On the basis of fish gill research, the biotic ligands appear to be active ion uptake pathways (e.g., Na+ transporters for copper and silver, Ca2+ transporters for zinc, cadmium, lead, and cobalt), whose geochemical characteristics (affinity = log K, capacity = Bmax) can be quantified in short-term (3-24 h) in vivo gill binding tests. In general, the greater the toxicity of a particular metal, the higher the log K. The BLM quantitatively relates short-term binding to acute toxicity, with the LA50 (lethal accumulation) being predictive of the LC50 (generally 96 h for fish, 48 h for daphnids). We critically evaluate currently available BLMs for copper, silver, zinc, and nickel and gill binding approaches for cadmium, lead, and cobalt on which BLMs could be based. Most BLMs originate from tests with fish and have been recalibrated for more sensitive daphnids by adjustment of LA50 so as to fit the results of toxicity testing. Issues of concern include the arbitrary nature of LA50 adjustments; possible mechanistic differences between daphnids and fish that may alter log K values, particularly for hardness cations (Ca2+, Mg2+); assumption of fixed biotic ligand characteristics in the face of evidence that they may change in response to acclimation and diet; difficulties in dealing with DOM and incorporating its heterogeneity into the modeling framework; and the paucity of validation exercises on natural water data sets. Important needs include characterization of biotic ligand properties at the molecular level; development of in vitro BLMs, extension of the BLM approach to a wider range of organisms, to the estuarine and marine environment, and to deal with metal mixtures; and further development of BLM frameworks to predict chronic toxicity and thereby generate chronic AWQC.

Cathode performance as a factor in electricity generation in microbial fuel cells

Abstract: Although microbial fuel cells (MFCs) generate much lower power densities than hydrogen fuel cells, the characteristics of the cathode can also substantially affect electricity generation. Cathodes used for MFCs are often either Pt-coated carbon electrodes immersed in water that use dissolved oxygen as the electron acceptor or they are plain carbon electrodes in a ferricyanide solution. The characteristics and performance of these two cathodes were compared using a two-chambered MFC. Power generation using the Pt-carbon cathode and dissolved oxygen (saturated) reached a maximum of 0.097 mW within 120 h after inoculation (wastewater sludge and 20 mM acetate) when the cathode was equal size to the anode (2.5 × 4.5 cm). Once stable power was generated after replacing the MFC with fresh medium (no sludge), the Coulombic efficiency ranged from 63 to 78%. Power was proportional to the dissolved oxygen concentration in a manner consistent with Monod-type kinetics, with a half saturation constant of KDO = 1.74 mg ...

Equivalence of elemental carbon by thermal/optical reflectance and transmittance with different temperature protocols.

Abstract: Charring of organic carbon (OC) during thermal/optical analysis is monitored by the change in a laser signal either reflected from or transmitted through a filter punch. Elemental carbon (EC) in suspended particulate matter collected on quartz-fiber filters is defined as the carbon that evolves after the detected optical signal attains the value it had prior to commencement of heating, with the rest of the carbon classified as organic carbon (OC). Heretofore, operational definitions of EC were believed to be caused by different temperature protocols rather than by the method of monitoring charring. This work demonstrates that thermal/ optical reflectance (TOR) corrections yield equivalent OC/ EC splits for widely divergent temperature protocols. EC results determined by simultaneous thermal/optical transmittance (TOT) corrections are 30% lower than TOR for the same temperature protocol and 70-80% lower than TOR for a protocol with higher heating temperatures and shorter residence times. This is true for 58 urban samples from Fresno, CA, as well as for 30 samples from the nonurban IMPROVE network that are individually dominated by wildfire, vehicle exhaust, secondary organic aerosol, and calcium carbonate contributions. Visual examination of filter darkening at different temperature stages shows that substantial charring takes place within the filter, possibly due to adsorbed organic gases or diffusion of vaporized particles. The filter transmittance is more influenced by the within-filter char, whereas the filter reflectance is dominated by charring of the near-surface deposit that appears to evolve first when oxygen is added to helium in the analysis atmosphere for these samples. The amounts of charred OC (POC) and EC are also estimated from incremental absorbance. Small amounts of POC are found to dominate the incremental absorbance. EC estimated from absorbance are found to agree better with EC from the reflectance charring correction than with EC from the transmittance charring correction.

Photochemical fate of sulfa drugs in the aquatic environment: sulfa drugs containing five-membered heterocyclic groups.

Abstract: The photochemical fate of five sulfa drugs with varying five-membered heterocyclic substituents (sulfamethoxazole, sulfisoxazole, sulfamethizole, sulfathiazole, and sulfamoxole) was investigated in aqueous solution. The rate of direct photolysis of these compounds is dependent upon the identity of the heterocyclic R group as well as the pH of the solution. Matrix deconvolution methods were employed to determine the absorption spectrum and photolysis rate of each protonation state (cationic, neutral, and anionic). From these data, quantum yields for direct photodegradation were calculated for each protonation state of the sulfa drugs. The quantum yields calculated range from <0.005 for the neutral state of sulfamethizole to 0.7 ± 0.3 for the protonated state of sulfisoxazole. The protonation state that is most photoreactive varies among the sulfa drugs and cannot be attributed to the rate of photon absorption. Products arising from the direct photolysis of the sulfa drugs were also investigated. For all th...

Defining bioavailability and bioaccessibility of contaminated soil and sediment is complicated.

Abstract: Laura Ehlers and Richard Luthy recently published an important A-page feature in ES&T in which they persuasively make the case that improving risk assessment and remediation rests on better understanding of bioavailability (1). Their article provided a concise summary of a major U.S. National Research Council (NRC) report called Bioavailability of Contaminants in Soils and Sediments: Processes, Tools and Applications (2). Despite consensus by scientists that bioavailability is indeed critical to the risk assessment process, Ehlers and Luthy note that the NRC report contains no explicit definition of bioavailability. Rather, the report defines bioavailability processes as the individual physical, chemical, and biological interactions that determine the exposure of organisms to chemicals associated with soils and sediments.

Photolytic Debromination of Decabromodiphenyl Ether (BDE 209)

Abstract: Polybrominated diphenyl ethers (PBDE) are commonly used flame retardants. During the past years, concerns have increased due to their occurrence in the environment and humans. In general, the concentrations of lower brominated (tetra-penta) diphenyl ethers in biota exceed those of the most heavily used product, decabromodiphenyl ether (DecaBDE). In this study, the photolytic debromination of DecaBDE has been investigated in order to study the formation of lower brominated diphenyl ethers. The time course of photolysis of DecaBDE was studied in toluene, on silica gel, sand, sediment and soil using artificial sunlight and on the natural matrices (sediment, soil, sand) also using natural sunlight. DecaBDE was photolytically labile and formed debromination products in all matrices studied. Nona- to tetraBDEs were formed as well as some PBDFs. The half-lives in toluene and on silica gel were less than 15 min, and half-lives on other matrices ranged between 40 and 200 h. No differences were seen in the debromination pattern of BDE congeners sequentially formed in the different matrices or under different light conditions. However, the debromination rates were strongly dependent on the matrix with longer half-lives on natural matrices than artificial ones.

Arsenic removal using mesoporous alumina prepared via a templating method.

Abstract: The health threat of arsenic is well-known, and the U.S. EPA recommends the maximum contaminant level to be 0.01 ppm or less for arsenic in drinking water. Therefore, advanced treatment processes are needed for finished water to meet the required regulations. Adsorption is considered to be a less expensive procedure that is safer to handle than precipitation, ion exchange, and membrane filtration. Activated alumina (AA) is the most commonly used adsorbent for the removal of arsenic from aqueous solutions. However, conventional porous solids including AA have ill-defined pore structures and, typically, low adsorption capacities and act in a kinetically slow manner. An ideal adsorbent should have uniformly accessible pores, an interlinked pore system, a high surface area, and physical and/or chemical stability. To meet this requirement, mesoprous alumina (MA) with a wide surface area (307 m2/g) and uniform pore size (3.5 nm) was prepared, and a spongelike interlinked pore system was developed through a post-hydrolysis method. The resulting MA was insoluble and stable within the range of pH 3-7. The maximum uptake of As(V) by MA was found to be 7 times higher [121 mg of As(V)/g and 47 mg of As(III)/ g] than that of conventional AA, and the kinetics of adsorption were also rapid with complete adsorption in less than 5 h as compared to the conventional AA (about 2 d to reach half of the equilibrium value). A desorption study using sodium hydroxide solutions (0.01-1 M) was conducted, and 0.05 M NaOH was found to be the most suitable desorption agent. More than 85% of the arsenic adsorbed to the MA was desorbed in less than 1 h. Several other activated aluminas with different pore properties were also tested. The results show that the surface area of the adsorbents does not greatly influence on the adsorption capacity. In fact, the key factor is a uniform pore size and an interlinked pore system. These studies show that MA with a wide surface area, uniform pore size, and interlinked pore system can be used as an efficient adsorbent for the removal of arsenic.

Removal of Natural Hormones by Nanofiltration Membranes: Measurement, Modeling, and Mechanisms

Abstract: The removal mechanisms of four natural steroid hormones-estradiol, estrone, testosterone, and progesterone-by nanofiltration (NF) membranes were investigated. Two nanofiltration membranes with quite different permeabilities and salt retention characteristics were utilized. To better understand hormone removal mechanisms, the membrane average pore size was determined from retention data of inert organic solutes of various molecular weights and a pore transport model that incorporates steric (size) exclusion and hindered convection and diffusion. Results indicate that, at the early stages of filtration, adsorption (or partitioning) of hormones to the membrane polymer is the dominant removal mechanism. Because the adsorptive capacity of the membrane is limited, the final retention stabilizes when the adsorption of hormones into the membrane polymer has reached equilibrium. At this later filtration stage, the overall hormone retention is lower than that expected based solely on the size exclusion mechanism. This behavior is attributed to partitioning and subsequent diffusion of hormone molecules in the membrane polymeric phase, which ultimately results in a lower retention. Hormone diffusion in the membrane polymeric matrix most likely depends on the size of the hormone molecule, hydrogen bonding of hormones to membrane functional groups, and hydrophobic interactions of the hormone with the membrane polymeric matrix.

Modeling Tetracycline Antibiotic Sorption to Clays

Abstract: Sorption interactions of three high-use tetracycline antibiotics (oxytetracycline, chlortetracycline, tetracycline) with montmorillonite and kaolinite clays were investigated undervaried pH and ionic strength conditions. Sorption edges were best described with a model that included cation exchange plus surface complexation of zwitterion forms of these compounds. Zwitterion sorption was accompanied by proton uptake, was more favorable on acidic clay, and was relatively insensitive to ionic strength effects. Calcium salts promoted oxytetracycline sorption at alkaline pHs likely by a surface-bridging mechanism. Substituent effects among the compounds in the tetracycline class had only minor effects on sorption edges and isotherms under the same solution pH and ionic strength conditions. At low ionic strength, greater sorption to montmorillonite than kaolinite was observed at all pHs tested, even after normalizing for cation exchange capacity. These results indicate that soil and sediment sorption models for tetracyclines, and other pharmaceuticals with similar chemistry, must account for solution speciation and the presence of other competitor ions in soil or sediment pore waters.

Degradation of Endocrine Disrupting Chemicals Bisphenol A, Ethinyl Estradiol, and Estradiol during UV Photolysis and Advanced Oxidation Processes

Abstract: The degradation of three endocrine disrupting chemicals (EDCs), bisphenol A, ethinyl estradiol, and estradiol, was investigated via ultraviolet (UV) radiation photolysis and the UV/hydrogen peroxide advanced oxidation process (AOP). These EDCs have been detected at low levels in wastewaters and surface waters in both the United States and European countries, can cause adverse effects on humans and wildlife via interactions with the endocrine system, and thus must be treated before entering the public drinking water supply. Because many EDCs can only be partially removed with conventional water treatment systems, there is a need to evaluate alternative treatment processes. For each EDC tested, direct UV photolysis quantum yields were derived for use with both monochromatic low-pressure (LP) UV lamps and polychromatic medium-pressure (MP) UV lamps and second-order hydroxyl radical rate constants were developed. These parameters were utilized to successfully model UV treatment of the EDCs in laboratory and natural waters. The polychromatic MP UV radiation source was more effective for direct photolysis degradation as compared to conventional LP UV lamps emitting monochromatic UV 254 nm radiation. However, in all cases the EDCs were more effectively degraded utilizing UV/H2O2 advanced oxidation as compared to direct UV photolysis treatment.

Distribution and Fate of HBCD and TBBPA Brominated Flame Retardants in North Sea Estuaries and Aquatic Food Webs

Abstract: Tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereoisomers (α-, β-, and γ-HBCD) were investigated in effluents from sewage treatment works, landfill leachates, sediments, and food web organisms of the North Sea basin. Residues were quantified by liquid chromatography−mass spectrometry. Both flame retardants were enriched in sewage sludges, where a maximum total (Σ) HBCD concentration of 9.1 mg/kg (dry weight; d.w.) was found; TBBPA was at levels of 102 μg/kg. Landfill leachates from The Netherlands showed up to 36 mg (ΣHBCD)/kg (d.w.). γ-HBCD dominated isomeric profiles in sediments, and concentrations were elevated near to a site of HBCD manufacture. α-HBCD was the primary congener detected in marine mammals; however, very few samples exhibited TBBPA. ΣHBCD ranged from 2.1 to 6.8 mg/kg (lipid weight; l.w.) in liver and blubber of harbor porpoises (Phocoena phocoena) and seals (Phoca vitulina). TBBPA levels in cormorant (Phalacrocorax carbo) livers were up to 1 order of magnitude lower comp...

Extraction of Heavy Metals from Soils Using Biodegradable Chelating Agents

Abstract: Metal pollution of soils is widespread across the globe, and the clean up of these soils is a difficulttask. One possible remediation technique is ex-situ soil washing using chelating agents. Ethylenediaminetetraacetic acid (EDTA) is a very effective chelating agent for this purpose but has the disadvantage that it is quite persistent in the environment due to its low biodegradability. The aim of our work was to investigate the biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDSA), methylglycine diacetic acid (MGDA), and nitrilotriacetic acid (NTA) as potential alternatives and compare them with EDTA for effectiveness. Kinetic experiments showed for all metals and soils that 24 h was the optimum extraction time. Longer times only gave minor additional benefits for heavy metal extraction but an unwanted increase in iron mobilization. For Cu at pH 7, the order of the extraction efficiency for equimolar ratios of chelating agent to metal was EDDS > NTA> IDSA > MGDA > EDTA and for Zn it was NTA > EDDS > EDTA >MGDA > IDSA. The comparatively low efficiency of EDTA resulted from competition between the heavy metals and co-extracted Ca. For Pb the order of extraction was EDTA > NTA >EDDS due to the much stronger complexation of Pb by EDTA compared to EDDS. At higher concentration of complexing agent, less difference between the agents was found and less pH dependence. There was an increase in heavy metal extraction with decreasing pH, but this was offset by an increase in Ca and Fe extraction. In sequential extractions EDDS extracted metals almost exclusively from the exchangeable, mobile, and Mn-oxide fractions. We conclude that the extraction with EDDS at pH 7 showed the best compromise between extraction efficiency for Cu, Zn, and Pb and loss of Ca and Fe from the soil.

Passive Air Sampling of PCBs, PBDEs, and Organochlorine Pesticides Across Europe

Abstract: This study presents concurrently sampled ambient air data for a range of persistent organic pollutants at the continental scale. This was achieved using a passive air sampling system, deploying polyurethane foam disks, which was prepared in one laboratory, sealed to prevent contamination, sent out by courier to volunteers participating in different countries, exposed for 6 weeks, collected, re-sealed, and returned to the laboratory for analysis. Europe was the study areaa region with a history of extensive POPs usage and emission and with marked national differences in population density, the degree of urbanization and industrial/agricultural development. Samplers were deployed at remote/rural/urban locations in 22 countries and analyzed for PCBs, a range of organochlorine pesticides (HCB, α-HCH, γ-HCH, ppDDT, ppDDE), and PBDEs. Calculated air concentrations were in line with those obtained by conventional active air sampling techniques. The geographical pattern of all compounds reflected suspected region...

Tire-wear particles as a source of zinc to the environment

Abstract: Tire-tread material has a zinc (Zn) content of about 1 wt %. The quantity of tread material lost to road surfaces by abrasion has not been well characterized. Two approaches were used to assess the magnitude of this nonpoint source of Zn in the U.S. for the period 1936−1999. In the first approach, tread-wear rates from the automotive engineering literature were used in conjunction with vehicle distance-driven data from the U.S. Department of Transportation to determine Zn releases. A second approach calculated this source term from the volume of tread lost during lifetime tire wear. These analyses showed that the quantity of Zn released by tire wear in the mid-1990s was of the same magnitude as that released from waste incineration. For 1999, the quantity of Zn released by tire wear in the U.S. is estimated to be 10 000−11 000 metric tons. A specific case study focused on Zn sources and sinks in an urban−suburban watershed (Lake Anne) in the Washington, DC, metropolitan area for a time period of the late ...

Bacterial adhesion and transport in porous media: role of the secondary energy minimum.

Abstract: The adhesion of a well-characterized Escherichia coli bacterial strain to quartz sediment grains in the presence of repulsive electrostatic interactions is systematically examined. An increase in the ionic strength of the pore fluid results in an increase in bacterial attachment, despite DLVO calculations indicating a sizable electrostatic energy barrier to deposition. Bacterial deposition is likely occurring in the secondary energy minimum, which DLVO calculations indicate increases in depth with ionic strength. A decrease in the ionic strength of the pore fluid--thereby eliminating the secondary energy minimum--resulted in release of the majority of previously deposited bacteria, suggesting that these cells were deposited reversibly in the secondary minimum. Additionally, bacterial attachment to a quartz surface in a radial stagnation point flow system was absent at ionic strengths less than 0.01 M and resulted in attachment efficiencies over an order of magnitude lower than in the packed-bed column experiments at higher ionic strengths. Because of the hydrodynamics in the radial stagnation point flow system, this observation supports our conclusion that the majority of bacterial deposition in the packed bed occurs in a secondary energy minimum.

Removal of Estrogens in Municipal Wastewater Treatment under Aerobic and Anaerobic Conditions: Consequences for Plant Optimization

Abstract: The removal of estrogens (estrone E1, estradiol E2, and ethinylestradiol EE2) was studied in various municipal wastewater treatment processes equipped for nutrient removal. A biological degradation model is formulated, and kinetic parameters are evaluated with batch experiments under various redox conditions. The resulting model calculations are then compared with sampling campaigns performed on different types of full-scale plant: conventional activated-sludge treatment, a membrane bioreactor, and a fixed-bed reactor. The results show a >90% removal of all estrogens in the activated sludge processes. (Due to the analytical quantification limit and low influent concentrations, however, this removal efficiency represents only an observable minimum.) The removal efficiencies of 77% and ≥90% for E1 and E2, respectively, in the fixed-bed reactor represent a good performance in view of the short hydraulic retention time of 35 min. The first-order removal-rate constant in batch experiments observed for E2 vari...