Influence of polymer type and carbon nanotube properties on carbon nanotube/polymer nanocomposite biodegradation.

The interaction of anaerobic microorganisms with carbon nanotube/polymer nanocomposites (CNT/PNC) will play a major role in determining their persistence and environmental fate at the end of consumer use when these nano-enabled materials enter landfills and encounter wastewater. Motivated by the need to understand how different parameters (i.e., polymer type, microbial phenotype, CNT characteristics) influence CNT/PNC biodegradation rates, we have used volumetric biogas measurements and kinetic modeling to study biodegradation as a function of polymer type and CNT properties. In one set of experiments, oxidized multiwall carbon nanotubes (O-MWCNTs) with a range of CNT loadings 0-5% w/w were incorporated into poly-ε-caprolactone (PCL) and polyhydroxyalkanoates (PHA) matrices and subjected to biodegradation by an anaerobic microbial community. For each CNT/PNC, complete polymer biodegradation was ultimately observed, although the rate of biodegradation was inhibited above certain critical CNT loadings dependent upon the polymer type. Higher loadings of pristine MWCNTs were needed to decrease the rate of polymer biodegradation compared to O-MWCNTs, an effect ascribed principally to differences in CNT dispersion within the polymer matrices. Above certain CNT loadings, a CNT mat of similar shape to the initial PNC was formed after polymer biodegradation, while below this threshold, CNT aggregates fragmented in the media. In situations where biodegradation was rapid, methanogen growth was disproportionately inhibited compared to the overall microbial community. Analysis of the results obtained from this study indicates that the inhibitory effect of CNTs on polymer biodegradation rate is greatest under conditions (i.e., polymer type, microbial phenotype, CNT dispersion) where biodegradation of the neat polymer is slowest. This new insight provides a means to predict the environmental fate, persistence, and transformations of CNT-enabled polymer materials.

Manganese-induced Parkinsonism in mice is reduced using a novel contaminated water sediment exposure model.

Heavy metals enter the aquatic environment and accumulate within water sediments, but these metal-sediment interactions remain to be explored within toxicity studies. We developed an exposure model in mice that encapsulates the aquatic microenvironment of metals before exposure. Male and female C57/BL6 mice were exposed via their drinking water to manganese contaminated sediment (Sed_Mn) or to manganese without sediment interaction (Mn) for six weeks. Sediment interaction did not alter weekly manganese ingestion from water in males or females. We analyzed motor impairment, a common feature in manganese-induced Parkinsonism, using the beam traversal, cylinder, and accelerating rotarod tests. Sed_Mn mice performed better overall compared to Mn mice and males were more sensitive to manganese than females in both Sed_Mn and Mn treatment groups. Our study indicates that metal-sediment interactions may alter metal toxicity in mammals and introduces a new exposure model to test the toxicity of metal contaminants of drinking water.

Sequential biodegradation of 1,2,4-trichlorobenzene at oxic-anoxic groundwater interfaces in model laboratory columns.

Halogenated organic solvents such as chlorobenzenes (CBs) are frequent groundwater contaminants due to legacy spills. When contaminated anaerobic groundwater discharges into surface water through wetlands and other transition zones, aeration can occur from various physical and biological processes at shallow depths, resulting in oxic-anoxic interfaces (OAIs). This study investigated the potential for 1,2,4-trichlorobenzene (1,2,4-TCB) biodegradation at OAIs. A novel upflow column system was developed to create stable anaerobic and aerobic zones, simulating a natural groundwater OAI. Two columns containing (1) sand and (2) a mixture of wetland sediment and sand were operated continuously for 295 days with varied doses of 0.14-1.4 mM sodium lactate (NaLac) as a model electron donor. Both column matrices supported anaerobic reductive dechlorination and aerobic degradation of 1,2,4-TCB spatially separated between anaerobic and aerobic zones. Reductive dechlorination produced a mixture of di- and monochlorobenzene daughter products, with estimated zero-order dechlorination rates up to 31.3 µM/h. Aerobic CB degradation, limited by available dissolved oxygen, occurred for 1,2,4-TCB and all dechlorinated daughter products. Initial reductive dechlorination did not enhance the overall observed extent or rate of subsequent aerobic CB degradation. Increasing NaLac dose increased the extent of reductive dechlorination, but suppressed aerobic CB degradation at 1.4 mM NaLac due to increased oxygen demand. 16S-rRNA sequencing of biofilm microbial communities revealed strong stratification of functional anaerobic and aerobic organisms between redox zones including the sole putative reductive dechlorinator detected in the columns, Dehalobacter. The sediment mixture column supported enhanced reductive dechlorination compared to the sand column at all tested NaLac doses and growth of Dehalobacter populations up to 4.1 × 108 copies/g (51% relative abundance), highlighting the potential benefit of sediments in reductive dechlorination processes. Results from these model systems suggest both substantial anaerobic and aerobic CB degradation can co-occur along the OAI at contaminated sites where bioavailable electron donors and oxygen are both present.

Production of lipid-containing algal-bacterial polyculture in wastewater and biomethanation of lipid extracted residues: Enhancing methane yield through hydrothermal pretreatment and relieving solvent toxicity through co-digestion.

The feasibility of generating a lipid-containing algal-bacterial polyculture biomass in municipal primary wastewater and enhancing biomethanation of lipid-extracted algal residues (LEA) through hydrothermal pretreatment and co-digestion with sewage sludge (SS) was investigated. In high-rate algal ponds, the polyculture of native algal and bacteria species demonstrated a monthly average net and gross biomass productivity of 30 ±â€¯3 and 36 ±â€¯3 gAFDW m-2 day-1 (summer season). The algal community was dominated by Micractinium sp. followed by Scenedesmus sp., Chlorella sp., pennate diatoms and Chlamydomonas sp. The polyculture metabolic activities resulted in average reductions of wastewater volatile suspended solids (VSS), carbonaceous soluble biochemical oxygen demand (csBOD5) and total nitrogen (Ntotal) of 63 ±â€¯18%, 98 ±â€¯1% and 76 ±â€¯21%, respectively. Harvested biomass contained nearly 23% lipid content and an extracted blend of fatty acid methyl esters satisfied the ASTM D6751 standard for biodiesel. Anaerobic digestion of lipid extracted algal residues (LEA) demonstrated long lag-phase in methane production of 17 days and ultimate methane yield of 296 ±â€¯2 mL/gVS (or ~50% of theoretical), likely because to its limited biodegradability and toxicity due to presence of the residual solvent (hexane). Hydrothermal pretreatment increased the ultimate methane yield and production rate by 15-30% but did not mitigate solvent toxicity effects completely leading to less substantial improvement in energy output of 5-20% and diminished Net Energy Ratio (NER < 1). In contrast, co-digestion of LEA with sewage sludge (10% to 90% ratio) was found to minimize solvent toxicity and improve methane yield enhancing the energy output ~4-fold, compared to using LEA as a single substrate, and advancing NER to 4.2.

Synergistic co-digestion of wastewater grown algae-bacteria polyculture biomass and cellulose to optimize carbon-to-nitrogen ratio and application of kinetic models to predict anaerobic digestion energy balance.

This study investigated enhancing methane production from algal-bacteria biomass by adjusting the C/N ratio through co-digestion with a nitrogen-poor co-substrate - cellulose. A biomethane potential test was used to determine cumulative biogas and methane production for pure and co-digested substrates. Four kinetic models were evaluated for their accuracy describing experimental data. These models were used to estimate the total energy output and net energy ratio (NER) for a scaled AD system. Increasing the algal C/N ratio from 5.7 to 20-30 (optimal algae:cellulose feedstock ratios of 35%:65% and 20%:80%) improved the ultimate methane yield by >10% and the first ten days production by >100%. The modified Gompertz kinetic model demonstrated highest accuracy, predicting that co-digestion improved methane production by reducing the time-lag by ∼50% and increasing rate by ∼35%. The synergistic effects increase the AD system energy efficiency and NER by 30-45%, suggesting potential for substantial enhancements from co-digestion at scale.

Biodegradability of carbon nanotube/polymer nanocomposites under aerobic mixed culture conditions.

The properties and commercial viability of biodegradable polymers can be significantly enhanced by the incorporation of carbon nanotubes (CNTs). The environmental impact and persistence of these carbon nanotube/polymer nanocomposites (CNT/PNCs) after disposal will be strongly influenced by their microbial interactions, including their biodegradation rates. At the end of consumer use, CNT/PNCs will encounter diverse communities of microorganisms in landfills, surface waters, and wastewater treatment plants. To explore CNT/PNC biodegradation under realistic environmental conditions, the effect of multi-wall CNT (MWCNT) incorporation on the biodegradation of polyhydroxyalkanoates (PHA) was investigated using a mixed culture of microorganisms from wastewater. Relative to unfilled PHA (0% w/w), the MWCNT loading (0.5-10% w/w) had no statistically significant effect on the rate of PHA matrix biodegradation. Independent of the MWCNT loading, the extent of CNT/PNC mass remaining closely corresponded to the initial mass of CNTs in the matrix suggesting a lack of CNT release. CNT/PNC biodegradation was complete in approximately 20 days and resulted in the formation of a compressed CNT mat that retained the shape of the initial CNT/PNC. This study suggests that although CNTs have been shown to be cytotoxic towards a range of different microorganisms, this does not necessarily impact the biodegradation of the surrounding polymer matrix in mixed culture, particularly in situations where the polymer type and/or microbial population favor rapid polymer biodegradation.

Biodegradation of Carbon Nanotube/Polymer Nanocomposites using a Monoculture.

The biodegradation rates of carbon nanotube (CNT)/ polymer nanocomposites (PNCs) containing poly-ε-caprolactone (PCL) were investigated using Pseudomonas aeruginosa, a microorganism commonly found in the environment. CNT/PCL nanocomposite mass loss profiles revealed that the rate of PCL matrix biodegradation decreased systematically as the CNT loading increased from 0.1 to 10% w/w. Addition of even a low CNT loading (<1% w/w) caused the CNT/PCL biodegradation rate constant to decrease by more than 50%. Similar trends in biodegradation rate were observed for both pristine and oxidized multiwall CNTs embedded in PCL. During PCL matrix biodegradation, CNT accumulation was observed at the surface of CNT/PCL nanocomposites and single particle inductively coupled-mass spectrometry experiments revealed no measurable CNT release to the culture fluid. Experimental data indicated that biodegradation proceeded as a result of biofilm formation on the CNT/PCL nanocomposites and decreased as a function of CNT loading due to the cytotoxicity of CNTs toward P. aeruginosa and the physical barrier presented by the surface-accumulated CNTs to the underlying PCL substrate. As the CNT loading in the CNT/PCL nanocomposites increased, the microbial proliferation of planktonic cells in the surrounding media also decreased as did the biodegradation rate of PCL samples present in the same reactors. Results from this study demonstrate that the inclusion of CNTs into polymer matrices could increase the environmental persistence of polymers in lakes, landfills, and surface waters.

Phytoremediation of agriculture runoff by filamentous algae poly-culture for biomethane production, and nutrient recovery for secondary cultivation of lipid generating microalgae.

An integrated system was implemented for water phytoremediation and biofuel production through sequential cultivation of filamentous algae followed by cultivation of lipid-producing microalgae Chlorella sorokiniana. Natural poly-culture of filamentous algae was grown in agricultural stormwater using the Algal Turf Scrubber®, harvested and subjected for lipid extraction and/or methane production using anaerobic digestion (AD). While filamentous algae lipid content was too low for feasible biodiesel production (<2%), both whole biomass and lipid-extracted algal residues (LEA) yielded ∼0.2LmethanepergVS at loading rates up to 5gVS/L-day. Importantly, essential macro-nutrients and trace elements captured from stormwater were released into the AD effluent as soluble nutrients and were successfully tested as fertilizer replacement for cultivation of lipid-accumulating C. sorokiniana in a subsequent stage. Accordingly, filamentous algae poly-culture was exploited for waste nutrient capturing and biofuel feedstock generation. These nutrients were recovered and reused as a concentrated supplement for potentially high-value microalgae.

Bioprospecting of microalgae for integrated biomass production and phytoremediation of unsterilized wastewater and anaerobic digestion centrate.

Eighteen microalgae, including two local isolates, were evaluated for their ability to grow and remove nutrients from unsterilized primary or secondary wastewater effluents as well as wastewater supplemented with nutrient-rich anaerobic digester centrate (ADC). Most of the tested species except several phylogenetically clustered Chlorella sorokiniana including local isolates and Scenedesmus strains were unable to grow efficiently. This may reflect the presence of certain genetic traits important for robust growth in the unsterilized wastewater. The maximum algal-specific growth rates and biomass density obtained in these bacterial-contaminated cultures were in the range of 0.8-1 day(-1) and 250-350 mg L(-1), respectively. ADC supplementation was especially helpful to biologically treated secondary effluent with its lower initial macronutrient and micronutrient content. As a result of algal growth, total nitrogen and orthophosphate levels were reduced by as much as 90 and 70 %, respectively. Biological assimilation was estimated to be the main mechanism of nitrogen removal in primary and secondary effluents with ammonia volatilization and bacterial nitrification-denitrification contributing for cultures supplemented with ADC. Assimilation by algae served as the principal mechanism of orthophosphate remediation in secondary wastewater cultures, while chemical precipitation appeared also to be important for orthophosphate removal in primary wastewater. Overall, cultivation of microalgae in primary and primary + 5 % ADC may be more favorable from an economical and sustainability perspective due to elimination of the costly and energy-intensive biological treatment step. These findings demonstrate that unsterilized wastewater and ADC can serve as critical nutrient sources for biomass generation and that robust microalgae can be potent players in wastewater phytoremediation.

Anaerobic digestion of lipid-extracted Auxenochlorella protothecoides biomass for methane generation and nutrient recovery.

This study evaluated methane production and nutrient recovery from industrially produced, lipid extracted algal biomass (LEA) of Auxenochlorella protothecoides using semi-continuous anaerobic digestion (AD) at different organic loading rates (OLRs) and hydraulic retention times (HRTs). It was shown, that AD can improve biofuel production efficiency and sustainability, especially for scaled processes, through up to 30% increase in energy generation (up to 0.25 L of methane per g of LEA volatile solids) and partial nutrient recovery and recycling. The nutrient recycling with the AD effluent may reduce the cost of the supplied fertilizers by up to 45%. However, methane production was limited to nearly 50% of theoretical maxima potentially due to biomass recalcitrance and inhibition effects from the residual solvent in the LEA. Therefore, further AD optimization is required to maximize methane yield and nutrient recovery as well as investigation and elimination of inhibition from solvent residues.

Influence of oxygenation on chromium redox reactions with manganese sulfide (MnS(s)).

Manganese sulfide (MnS(s)) minerals exist in sulfidic environments and can have unique reactive abilities because of sulfide, which is a known reductant, and Mn, the oxyhydroxides of which are known oxidants. This study elucidated the role of MnS(s) in controlling Cr speciation with implications on its fate and toxicity in the natural environment, specifically sulfidic sediments that undergo biogeochemical changes due to sediment resuspension during dredging, bioturbation, and flood events. In continuously mixed batch reaction experiments, aqueous CrVI reduction under anaerobic conditions occurred primarily on the surface of MnS(s) displaying a biphasic behavior- the initial rapid removal of CrVI from solution was followed by a slow decline due to surface passivation by reaction products, mainly sorbed or precipitated CrIII. The reaction progress increased with MnS(s) surface area loading but decreased on increasing CrVI concentration and pH, suggesting that surface site regeneration through product desorption was the rate-controlling mechanism. Below circum-neutral pH, higher solubility of MnS(s) resulted in additional CrVI reduction by reduced sulfur species in solution, whereas increased CrIII solubility lowered surface passivation allowing for more reactive sites to participate in the reaction. Aeration of MnS(s) at pH≥7 caused the formation of a heterogeneous MnIII(hydr)oxide that was composed of hausmanite and manganite. CrVI reoccurrence was observed on aeration of CrVI-spiked MnS(s) from the oxidation of product CrIII. The reoccurrence at pH≥7 was attributed to the oxidation of product CrIII by MnIII(hydr)oxide, whereas the reoccurrence at pH<7 was hypothesized from the oxidation of product CrIII by intermediate aqueous MnIII and/or sulfur species. Just as with Cr, MnS(s) may play an important role in speciation, fate, and transport of other environmental contaminants.

Coupled effects of chemotaxis and growth on traveling bacterial waves.

Traveling bacterial waves are capable of improving contaminant remediation in the subsurface. It is fairly well understood how bacterial chemotaxis and growth separately affect the formation and propagation of such waves. However, their interaction is not well understood. We therefore perform a modeling study to investigate the coupled effects of chemotaxis and growth on bacterial migration, and examine their effects on contaminant remediation. We study the waves by using different initial electron acceptor concentrations for different bacteria and substrate systems. Three types of traveling waves can occur: a chemotactic wave due to the biased movement of chemotactic bacteria resulting from metabolism-generated substrate concentration gradients; a growth/decay/motility wave due to a dynamic equilibrium between bacterial growth, decay and random motility; and an integrated wave due to the interaction between bacterial chemotaxis and growth. Chemotaxis hardly enhances the bacterial propagation if it is too weak to form a chemotactic wave or its wave speed is less than half of the growth/decay/motility wave speed. However, chemotaxis significantly accelerates bacterial propagation once its wave speed exceeds the growth/decay/motility wave speed. When convection occurs, it speeds up the growth/decay/motility wave but slows down or even eliminates the chemotactic wave due to the dispersion. Bacterial survival proves particularly important for bacterial propagation. Therefore we develop a conceptual model to estimate the speed of growth/decay/motility waves.

Mineral and non-carbon nutrient utilization and recovery during sequential phototrophic-heterotrophic growth of lipid-rich algae.

A critical factor in implementing microalgal biofuels for mass production is the nutrient requirements. The current study investigated the fate of macro- and micronutrients and their availability in a sequential phototrophic-heterotrophic production process for the lipid rich microalga Auxenochlorella protothecoides. More than 99 % (by weight) of overall process nutrients were supplied during the initial photoautotrophic stage reflecting its significantly larger volume. Under photoautotrophic growth conditions only 9-35 % of supplied Mn, S, Fe, N, Mg, and Cu and less than 5 % of P, Mo, Co, B, Zn, and Ca were consumed by the algae. The rest of these nutrients remain in the spent growth media during the culture concentration-down from an 800 L phototrophic pond to a 5 L heterotrophic fermenter. In contrast, Zn, Mo, Mn, Mg, Ca, and N were exhausted (90-99 % removal) during the first 25 h of the heterotrophic growth stage. The depletion of these key nutrients may have ultimately limited the final biomass density and/or lipid productivity achieved. Approximately 10-20 % of the total supplied S, Mn, Fe, N, and Cu and 5 % of Ca and Zn were assimilated into algal biomass. Several elements including N, P, Mn, B, Cu, Ca, Mg, S, and Fe were released back into the liquid phase by anaerobic digestion (AD) of the residual biomass after lipid extraction. The nutrients recovered from the AD effluent and remaining in the spent medium should be recycled or their initial concentration to the phototrophic stage decreased to enhance process economics and sustainability for future commercialization of algal-derived biofuels.

Removal of pharmaceuticals and personal care products during water recycling: microbial community structure and effects of substrate concentration.

Many pharmaceuticals and personal care products (PPCPs) have been shown to be biotransformed in water treatment systems. However, little research exists on the effect of initial PPCP concentration on PPCP biotransformation or on the microbial communities treating impacted water. In this study, biological PPCP removal at various concentrations was assessed using laboratory columns inoculated with wastewater treatment plant effluent. Pyrosequencing was used to examine microbial communities in the columns and in soil from a soil aquifer treatment (SAT; a method of water treatment prior to reuse) site. Laboratory columns were supplied with different concentrations (0.25, 10, 100, or 1,000 µg liter(-1)) of each of 15 PPCPs. Five PPCPs (4-isopropyl-3-methylphenol [biosol], p-chloro-m-xylenol, gemfibrozil, ketoprofen, and phenytoin) were not removed at any tested concentrations. Two PPCPs (naproxen and triclosan) exhibited removals independent of PPCP concentration. PPCP removal efficiencies were dependent on initial concentrations for biphenylol, p-chloro-m-cresol, chlorophene, diclofenac, 5-fluorouracil, ibuprofen, and valproic acid, showing that PPCP concentration can affect biotransformation. Biofilms from sand samples collected from the 0.25- and 10-µg liter(-1) PPCP columns were pyrosequenced along with SAT soil samples collected on three consecutive days of a wetting and drying cycle to enable comparison of these two communities exposed to PPCPs. SAT communities were similar to column communities in taxonomy and phylotype composition, and both were found to contain close relatives of known PPCP degraders. The efficiency of biological removal of PPCPs was found to be dependent on the concentration at which the contamination occurs for some, but not all, PPCPs.

The effects of alternative pretreatment strategies on anaerobic digestion and methane production from different algal strains.

The effect of various pretreatment strategies on methane yields following anaerobic digestion (AD) of five different microalgal strains was investigated. Pavlova_cf sp., Tetraselmis sp. and Thalassiosira weissflogii exhibited substantial methane yields of 0.4-0.5L/g volatile solids (VS) without pretreatment, providing up to 75-80% of theoretical values. In contrast, methane yields from Chlorella sp. and Nannochloropsis sp. were around 0.35L/g VS, or 55-60% of the theoretical values, respectively. Alkali treatment was not effective and thermal pretreatment only enhanced Nannochloropsis methane yields. Thermochemical pretreatment had the strongest impact on biomass solubilization with methane yields increasing by 30% and 40% for Chlorella and Nannochloropsis, respectively. The lipid content had a strong beneficial impact on the theoretical and observed methane yields as compared to protein and carbohydrate content. Other features such as cell-wall composition are also likely to be important factors dictating algal biodegradability and methane yields addressed in part by thermochemical pretreatment.

Biogeochemical controls on hexavalent chromium formation in estuarine sediments.

Predicting the aquatic and human health impacts of chromium (Cr) necessitates one to determine its speciation as either relatively nontoxic Cr(III) or toxic Cr(VI) and elucidate the influence of biogeochemical changes on its behavior and fate. In the Baltimore Harbor, Cr predominantly exists as Cr(III) associated with sediments. While reduction of Cr(VI) to Cr(III) is dominant in these anoxic sediments, the potential of Cr(III) oxidation and Cr(VI) reoccurrence during sediment resuspension and oxygenation resulting from dredging, bioturbation, and flood events poses a serious concern. In batch experiments, aqueous Cr(VI) spiked into continuously mixed anoxic suspensions was reduced to product Cr(III) under anaerobic conditions. No Cr(VI) reoccurrence was observed when conditions remained anaerobic. Aeration caused Cr(VI) reoccurrence from the abiotic oxidation of product Cr(III). Rates of aeration-driven Cr(VI) reoccurrence increased with pH, and Cr(VI) reoccurrence positively correlated with dissolved manganese (Mn) decline at pH ≥ 7. Aeration-driven oxidation of Mn(II) to Mn(III,IV)(hydr)oxides was the underlying mechanism causing product Cr(III) oxidation. Cr(VI) reoccurrence decreased with sediment loading and negatively correlated with the acid volatile sulfide (AVS) concentration. Although sediment resuspension and oxygenation may create temporary conditions conducive to Cr(VI) formation, long-term Cr(VI) persistence is unlikely in the presence of sediment reductants. While such natural attenuation in reducing environments mitigates the risk associated with Cr toxicity, this risk may still persist in Mn-rich and reductant-deficient environments.

Bioaccumulation and biomagnification of mercury and selenium in the Sarasota Bay ecosystem.

The bioaccumulation and biomagnification of Hg and Se were investigated in Sarasota Bay, Florida, USA, to characterize the Hg exposure risks to wild bottlenose dolphins in the bay. Concentrations of total mercury (THg), monomethylmercury (MMHg), and total selenium (TSe) were monitored in the bay, the latter of which might reduce Hg toxicity. The food web structure and dolphins' trophic level-specific consumption rates were evaluated using stable isotope ratios of carbon (δ(13) C) and nitrogen (δ(15) N). Regressions developed for Hg biomagnification in the food chain were log10 CTHg (nanograms per gram) =0.27 × Î´(15) N (‰) - 0.42, R(2) =0.87, for THg and log10 CMMHg =0.33 × Î´(15) N (‰) - 1.0, R(2) =0.93, for MMHg. Unlike Hg, nearly constant TSe concentrations were observed at 248 ± 179 ng g(-1) in the food web, and the TSe-to-THg molar ratio was predicted by log10 (CTSe /CTHg ) = -0.10 × Î´(15) N (‰) +2.8, R(2) =0.60. The THg-uptake rates of Sarasota bottlenose dolphins are estimated to vary between 2.1 and 4.9 µg kg(-1) d(-1) ; however, the estimated TSe-uptake rates (15.1 µg kg(-1) d(-1) ) were higher than those for THg, and the Hg-exposure risks of the Sarasota Bay resident bottlenose dolphins are considered to be low. Approaches employed in the present study can be extended to other environments to characterize Hg contamination in aquatic systems and Hg exposure risks in top predators.

Biological removal of pharmaceuticals and personal care products during laboratory soil aquifer treatment simulation with different primary substrate concentrations.

Pharmaceuticals and personal care products (PPCPs) have been detected in bodies of water worldwide, yet their effects on the environment are not fully understood. Recent toxicity studies suggest that mixtures of PPCPs at low concentrations may be detrimental to exposed organisms, highlighting the need to remove PPCPs from wastewater treatment plant effluent before it is discharged to the environment. In this study, the utility of biofilm-based PPCP removal as a means to prevent environmental PPCP contamination was investigated. The removal of 14 PPCPs, each at an initial concentration of 10 µg/L, was studied in laboratory sand columns inoculated with wastewater treatment plant effluent. The examined PPCPs included biosol, biphenylol, p-chloro-m-cresol, p-chloro-m-xylenol, chlorophene, sodium diclofenac, gabapentin, gemfibrozil, 5-fluorouracil, ibuprofen, ketoprofen, naproxen, triclosan, and valproic acid. Ten of the PPCPs were removed by greater than 95% during column passage, while the four other compounds proved more recalcitrant. The effect of the concentration (either 50 or 1000 µg/L) of an easily degradable primary substrate (acetate) supplied along with the mixture of PPCPs was examined. Most of the tested PPCPs were removed consistently by the biofilms regardless of the concentration of acetate, although the extent of removal for three compounds showed dependence on acetate concentration, and two behaved with no reproducible pattern over time. Biofilm protein measurements indicated that the mixture of PPCPs supplied to columns suppressed biofilm growth, suggesting toxicity of the PPCPs to the biofilm communities. This laboratory-scale experiment suggests that biofilm-based water treatment strategies, such as soil aquifer treatment and slow sand filtration, may be well-suited for the removal of many PPCPs from impacted water.

Determination of pharmaceuticals and antiseptics in water by solid-phase extraction and gas chromatography/mass spectrometry: analysis via pentafluorobenzylation and stable isotope dilution.

A sensitive yet robust analytical method is presented for the simultaneous determination of 12 human pharmaceuticals (valproic acid, phenytoin, ibuprofen, gabapentin, acetaminophen, gemfibrozil, naproxen, ketoprofen, secobarbital, phenobarbital, 5-fluorouracil, and diclofenac) and 6 antiseptics (biosol, biphenylol, p-chloro-m-cresol, p-chloro-m-xylenol, chlorophene, and triclosan). The method employs solid-phase extraction (SPE) followed by a novel pentafluorobenzylation using a mixture of acetontrile/water (1/1, v/v). The method is simple to perform (derivatization can be completed in a single test tube) and eliminates the need for any solvent/SPE cartridge drying or blow-down. It affords excellent resolution, high sensitivity and reproducibility, and freedom from interference even for matrices as complex as untreated sewage. The method was applied to the analysis of sewage samples using 15 isotopically labeled surrogates, which resulted in the detection of 10 of the 12 pharmaceuticals and all of the antiseptics sought. Ten of 15 surrogates were synthesized from pure analytes by a simple H-D exchange reaction employing D(2)O and D(2)SO(4). Measured recoveries were sensitive to matrix effects and varied substantially among analytes, indicative of the limitations associated with using a single surrogate standard.

Assessment of mercury and selenium concentrations in captive bottlenose dolphin's (Tursiops truncatus) diet fish, blood, and tissue.

Concentrations of total mercury (Hg) and selenium (Se) were determined in diet fish and whole blood and tissue samples from seven bottlenose dolphins (Tursiops truncatus) housed at the National Aquarium Baltimore (NAB). In addition, concentrations of monomethylmercury (CH(3)Hg(+)) were determined in diet fish and dolphins' tissue samples. The data were compared with the values found in wild populations to better understand how the dietary Hg and Se uptake rates affect the Hg and Se levels in dolphins. The diet fish total Hg concentrations ranged between 14 and 47 ng g(-1) and were markedly lower than for similar fish found in Florida, South Carolina, and other aquaria. CH(3)Hg(+) accounted for 85 to 91% of the total Hg found in diet fish. The diet fish Se concentrations ranged between 270 and 800 ng g(-1), indicating excess molar concentrations of Se over Hg. The Hg concentration range in the blood of NAB dolphins was 27-117 ng g(-1) and the concentrations were about one order of magnitude and several factors lower than the concentrations found in the blood of wild bottlenose dolphins in Florida and in South Carolina, respectively. The total Hg and CH(3)Hg(+) in tissue samples were also significantly lower than the reported values obtained from wild populations of bottlenose dolphins. The differences in the Hg concentrations in the dolphins' blood may be due to the different levels of Hg atmospheric deposition in the area where the dolphins' diet fish were found. The Se concentration range in the blood of NAB dolphins was 221-297 ng g(-1) which was two factors lower than the values found in wild populations. The lower Hg levels, as well as higher Se:Hg molar ratios in the blood of NAB dolphins, suggest that NAB dolphins may be less susceptible to the potential neurotoxicity from the CH(3)Hg(+) in their blood.