Heather N. Bischel

Binding of perfluorocarboxylates to serum albumin: a comparison of analytical methods.

Perfluorochemicals are globally pervasive contaminants that are persistent, bioaccumulative, and toxic. Perfluorocarboxylic acids (PFCAs) with 8-13 carbons accumulate in the liver and blood of aquatic organisms; PFCA-protein interactions may explain this accumulation pattern. Here, the interactions between PFCAs with 8-11 carbons and serum albumin are examined using three experimental approaches: surface tension titrations, (19)F NMR spectroscopy, and fluorescence spectroscopy. Surface tension titrations indicate complex formation at high (mM) PFCA concentrations. Secondary association constants ranging from 10(2) to 10(4) M(-1) were determined from (19)F NMR titrations at high PFCA:albumin mole ratios. Fluorescence measurements indicate that PFCA-albumin interactions alter the protein conformation at low PFCA:albumin mole ratios (up to 5:1) and suggest two binding classes with association constants around 10(5) and 10(2) M(-1). While (19)F NMR and fluorescence provide both qualitative and quantitative information about PFCA-albumin interactions, surface tension provides only qualitative information. Limitations associated with instrumentation and methods require high PFCA concentrations in both surface tension and (19)F NMR experiments; in contrast, fluorescence allows for analysis of a wider range of PFCA concentrations and PFCA:albumin mole ratios. Results from this study indicate that fluorescence, though an indirect method, offers a more comprehensive picture of the nature of PFCA-albumin interactions.

Noncovalent Interactions of Long-Chain Perfluoroalkyl Acids with Serum Albumin

Preferential distribution of long-chain perfluoroalkyl acids (PFAAs) in the liver, kidney, and blood of organisms highlights the importance of PFAA-protein interactions in PFAA tissue distribution patterns. A serum protein association constant may be a useful parameter to characterize the bioaccumulative potential and in vivo bioavailability of PFAAs. In this work, association constants (K(a)) and binding stoichiometries for PFAA-albumin complexes are quantified over a wide range of PFAA:albumin mole ratios. Primary association constants for perfluorooctanoate (PFOA) or perfluorononanoate (PFNA) with the model protein bovine serum albumin (BSA) determined via equilibrium dialysis are on the order of 10(6) M(-1) with one to three primary binding sites. PFNA was greater than 99.9% bound to BSA or human serum albumin (HSA) at a physiological PFAA:albumin mole ratio (<10(-3)), corresponding to a high protein-water distribution coefficient (log K(PW) > 4). Nanoelectrospray ionization mass spectrometry (nanoESI-MS) data reveal PFAA-BSA complexes with up to eight occupied binding sites at a 4:1 PFAA:albumin mole ratio. Association constants estimated by nanoESI-MS are on the order of 10(5) M(-1) for PFOA and PFNA and 10(4) M(-1) for perfluorodecanoate and perfluorooctanesulfonate. The results reported here suggest binding through specific high affinity interactions at low PFAA:albumin mole ratios.

Strong associations of short‐chain perfluoroalkyl acids with serum albumin and investigation of binding mechanisms

Interactions of perfluoroalkyl acids (PFAAs) with tissue and serum proteins likely contribute to their tissue distribution and bioaccumulation patterns. Protein-water distribution coefficients (K(PW) ) based on ligand associations with bovine serum albumin (BSA) as a model protein were recently proposed as biologically relevant parameters to describe the environmental behavior of PFAAs, yet empirical data on such protein binding behavior are limited. In the present study, associations of perfluoroalkyl carboxylates (PFCAs) with two to 12 carbons (C₂-C₁₂) and perfluoroalkyl sulfonates with four to eight carbons (C₄, C₆, and C₈) with BSA are evaluated at low PFAA:albumin mole ratios and various solution conditions using equilibrium dialysis, nanoelectrospray ionization mass spectrometry, and fluorescence spectroscopy. Log K(PW) values for C₄ to C₁₂ PFAAs range from 3.3 to 4.3. Affinity for BSA increases with PFAA hydrophobicity but decreases from the C₈ to C₁₂ PFCAs, likely due to steric hindrances associated with longer and more rigid perfluoroalkyl chains. The C₄-sulfonate exhibits increased affinity relative to the equivalent chain-length PFCA. Fluorescence titrations support evidence that an observed dependence of PFAA-BSA binding on pH is attributable to conformational changes in the protein. Association constants determined for perfluorobutanesulfonate and perfluoropentanoate with BSA are on the order of those for long-chain PFAAs (K(a) ∼10⁶/M), suggesting that physiological implications of strong binding to albumin may be important for short-chain PFAAs.

Management experiences and trends for water reuse implementation in Northern California.

In 2010, California fell nearly 300,000 acre-ft per year (AFY) short of its goal to recycle 1,000,000 AFY of municipal wastewater. Growth of recycled water in the 48 Northern California counties represented only 20% of the statewide increase in reuse between 2001 and 2009. To evaluate these trends and experiences, major drivers and challenges that influenced the implementation of recycled water programs in Northern California are presented based on a survey of 71 program managers conducted in 2010. Regulatory requirements limiting discharge, cited by 65% of respondents as a driver for program implementation, historically played an important role in motivating many water reuse programs in the region. More recently, pressures from limited water supplies and needs for system reliability are prevalent drivers. Almost half of respondents (49%) cited ecological protection or enhancement goals as drivers for implementation. However, water reuse for direct benefit of natural systems and wildlife habitat represents just 6-7% of total recycling in Northern California and few financial incentives exist for such projects. Economic challenges are the greatest barrier to successful project implementation. In particular, high costs of distribution systems (pipelines) are especially challenging, with

Economic and Ecological Costs and Benefits of Streamflow Augmentation Using Recycled Water in a California Coastal Stream

1 to 3 million/mile costs experienced. Negative perceptions of water reuse were cited by only 26% of respondents as major hindrances to implementation of surveyed programs.

Pathogens and pharmaceuticals in source-separated urine in eThekwini, South Africa.

Streamflow augmentation has the potential to become an important application of recycled water in water scarce areas. We assessed the economic and ecological merits of a recycled water project that opted for an inland release of tertiary-treated recycled water in a small stream and wetland compared to an ocean outfall discharge. Costs for the status-quo scenario of discharging secondary-treated effluent to the ocean were compared to those of the implemented scenario of inland streamflow augmentation using recycled water. The benefits of the inland-discharge scenario were greater than the increase in associated costs by US

Recycled water for augmenting urban streams in mediterranean-climate regions: a potential approach for riparian ecosystem enhancement

1.8M, with recreational value and scenic amenity generating the greatest value. We also compared physical habitat quality, water quality, and benthic macroinvertebrate community upstream and downstream of the recycled water discharge to estimate the effect of streamflow augmentation on the ecosystem. The physical-habitat quality was higher downstream of the discharge, although streamflow came in unnatural diurnal pulses. Water quality remained relatively unchanged with respect to dissolved oxygen, pH, and ammonia-nitrogen, although temperatures were elevated. Benthic macroinvertebrates were present in higher abundances, although the diversity was relatively low. A federally listed species, the California red-legged frog (Rana draytonii), was present. Our results may support decision-making for wastewater treatment alternatives and recycled water applications in Mediterranean climates.

Oceans and Human Health

In eThekwini, South Africa, the production of agricultural fertilizers from human urine collected from urine-diverting dry toilets is being evaluated at a municipality scale as a way to help finance a decentralized, dry sanitation system. The present study aimed to assess a range of human and environmental health hazards in source-separated urine, which was presumed to be contaminated with feces, by evaluating the presence of human pathogens, pharmaceuticals, and an antibiotic resistance gene. Composite urine samples from households enrolled in a urine collection trial were obtained from urine storage tanks installed in three regions of eThekwini. Polymerase chain reaction (PCR) assays targeted 9 viral and 10 bacterial human pathogens transmitted by the fecal-oral route. The most frequently detected viral pathogens were JC polyomavirus, rotavirus, and human adenovirus in 100%, 34% and 31% of samples, respectively. Aeromonas spp. and Shigella spp. were frequently detected gram negative bacteria, in 94% and 61% of samples, respectively. The gram positive bacterium, Clostridium perfringens, which is known to survive for extended times in urine, was found in 72% of samples. A screening of 41 trace organic compounds in the urine facilitated selection of 12 priority pharmaceuticals for further evaluation. The antibiotics sulfamethoxazole and trimethoprim, which are frequently prescribed as prophylaxis for HIV-positive patients, were detected in 95% and 85% of samples, reaching maximum concentrations of 6800 μg/L and 1280 μg/L, respectively. The antiretroviral drug emtricitabine was also detected in 40% of urine samples. A sulfonamide antibiotic resistance gene (sul1) was detected in 100% of urine samples. By coupling analysis of pathogens and pharmaceuticals in geographically dispersed samples in eThekwini, this study reveals a range of human and environmental health hazards in urine intended for fertilizer production. Collection of urine offers the benefit of sequestering contaminants from environmental release and allows for targeted treatment of potential health hazards prior to agricultural application. The efficacy of pathogen and pharmaceutical inactivation, transformation or removal during urine nutrient recovery processes is thus briefly reviewed.

Tracking and Modeling the Degradation of a 30 Year Old Fuel Oil Spill with Comprehensive Two-Dimensional Gas Chromatography

Abstract The scarcity of water in mediterranean-climate regions makes flow management in the rehabilitation of urban streams problematic. To explore potential applications of using recycled water for stream enhancement, we examine streams in the San Francisco Bay Area of California, USA, to characterize: (a) historic flow regimes at the regional scale, (b) potential unintended ecological effects and (c) specific issues related to recycled water. We analysed historic flow regimes in five basins, performed a streamflow augmentation experiment and monitored benthic macroinvertebrates above and below a recycled-water discharge. Streamflow augmentation with recycled water can provide improved aesthetics and aquatic habitat, but there are caveats to consider. Implications of inputs of recycled water in streams, whether direct or indirect, require detailed analysis of trade-offs. Augmentation is unlikely to harm the ecology of urban streams that are now just barely flowing perennially with pools of stagnant, contaminated water, and it may reduce public health problems from mosquitoes. Editor Z.W. Kundzewicz; Guest editor M. Acreman Citation Lawrence, J.E., Pavia, C.P.W., Kaing, S., Bischel, H.N., Luthy, R.G., and Resh, V.H., 2014. Recycled water for augmenting urban streams in mediterranean-climate regions: a potential approach for riparian ecosystem enhancement. Hydrological Sciences Journal, 59 (3–4), 488–501.

Issues of Governance, Policy, and Law in Managing Urban–Rural and Groundwater–Surface Water Connections

The oceans contain chemicals and microscopic organisms that represent both risks and remedies to humans. Harmful algae including dinoflagellates, diatoms, and cyanobacteria excrete toxins that may bioaccumulate in fish and shellfish. When consumed by humans, these toxins cause ailments such as gastrointestinal illness and diseases as serious as Parkinson disease. Anthropogenic activities have released harmful persistent organic compounds and metals into the environment. Human exposure to these chemicals via shellfish, fish, or even contaminated sediments can cause chronic and acute illness. Transient and autochthonous pathogens in the marine environment emanate from sewage or are natural members of marine microbial communities, respectively. Contact with pathogens in marine waters represents health risks to swimmers as well as seafood consumers. Global climate change is expected to have harmful, although poorly understood, impacts on human well-being. At the same time, many secondary metabolites of sea organisms are being exploited as remedies for serious human illnesses and symptoms.