Aria Amirbahman

Kinetics of cadmium uptake by chitosan-based crab shells

Crushed crab shells were chemically treated to transform the chitin present into chitosan. Three particle sizes with average diameters of 0.65, 1.43 and 3.38 mm, average pore diameters ranging from approximately 300 to 540 A, and a specific surface area of approximately 30 m2/g were obtained. Batch experiments were performed to study the uptake equilibrium and kinetics of cadmium by chitosan. Adsorption equilibrium followed a Freundlich relationship and was found to be independent of particle size indicating that adsorption takes place largely in the pore space. A high initial rate of cadmium uptake was followed by a slower uptake rate suggesting intraparticle diffusion as the rate-limiting step. The kinetic uptake data were successfully modeled using a pore diffusion model incorporating nonlinear adsorption. The effect of boundary layer resistance was modeled through inclusion of a mass transfer expression at the outside boundary. Two fitting parameters, the tortuosity factor (tau) and the mass transfer coefficient at the outside boundary (k(c)) were used. These parameters were unique for all solute and sorbent concentrations. The tortuosity factors varied from 1.5 for large particles to 5.1 for small particles. The mass transfer coefficient varied from 2 x 10(-7) m/s at 50 rpm to 2 x 10(-3) m/s at 200 rpm. At agitation rates below 100 rpm, boundary layer resistance reduced the uptake rate significantly. Its very high sorption capacity and relatively low production cost make chitosan an attractive sorbent for the removal of heavy metals from waste streams.

Methylmercury in Marine Ecosystems: Spatial Patterns and Processes of Production, Bioaccumulation, and Biomagnification

The spatial variation of MeHg production, bioaccumulation, and biomagnification in marine food webs is poorly characterized but critical to understanding the links between sources and higher trophic levels, such as fish that are ultimately vectors of human and wildlife exposure. This article discusses both large and local scale processes controlling Hg supply, methylation, bioaccumulation, and transfer in marine ecosystems. While global estimates of Hg supply suggest important open ocean reservoirs of MeHg, only coastal processes and food webs are known sources of MeHg production, bioaccumulation, and bioadvection. The patterns observed to date suggest that not all sources and biotic receptors are spatially linked, and that physical and ecological processes are important in transferring MeHg from source regions to bioaccumulation in marine food webs and from lower to higher trophic levels.

Relationship between hypolimnetic phosphorus and iron release from eleven lakes in Maine, USA

We studied five eutrophic (high phosphorus) and six mesotrophic/oligotrophic (low phosphorus) lakes in Maine, USA, all of which are dimictic and develop anoxic hypolimnia during stratification. The lakes were sampled during the stratified period from May to September 1999. Late summer hypolimnetic total phosphorus (P) concentrations in the high-P lakes ranged from 185 to 460 ppb; epilimnetic total P increased up to 30 ppb from the spring to the fall overturn. During the same period, the low-P lakes had hypolimnetic total P concentrations in the range of 6–19 ppb.Individual high-P lakes demonstrated strong temporal correlations between aqueous hypolimnetic dissolved Fe and total P concentrations (R2 ≥ 0.88) with an average molar Fe:P ratio of 11.9 ± 4.2. For the combined data, the high-P lakes exhibited strong correlation between hypolimnetic Fe and P concentrations (R2 = 0.82). The low-P lakes, however, did not show a good correlation between the hypolimnetic Fe and P concentrations. Among the low-P lakes two lakes had hypolimnetic Fe fluxes comparable to the Fe fluxes of the high-P lakes. These two lakes had considerably higher hypolimnetic Fe:P ratios than all other lakes studied here. There were no significant differences in surface sediment Fe(III) or P fractions that correlated with the differences in the relationship between aqueous concentrations of Fe and P in these two outlier low-P lakes. A model for the generation of hypolimnetic acid neutralization capacity (ANC) was developed based on microbially-catalyzed reduction of Fe(III) hydroxide, Mn(IV) oxide and sulfate. Reduction of Fe(III) hydroxide was the most important contributor to the increase in the hypolimnetic ANC in all high-P and the two outlier lakes. Assuming that all hypolimnetic P was due to the reduction of Fe(III) hydroxide by bacteria and sulfide, average summer hypolimnetic P flux for each lake was predicted using the sediment reducible Fe(III):P ratio. The observed and predicted average P fluxes in the high-P lakes corresponded reasonably, suggesting that in these lakes internal P release is closely related to the reduction of Fe(III) hydroxide. Other release or sequestration mechanisms may operate for the release and availability of P in the low-P lakes.

The effect of fire on mercury cycling in the soils of forested watersheds: Acadia National Park, Maine, U.S.A

This study compares mercury (Hg) and methylmercury (MeHg) distribution in the soils of two forested stream watersheds at Acadia National Park, Maine, U.S.A. Cadillac Brook watershed, which burned in 1947, has thin soils and predominantly deciduous vegetation. It was compared to the unburned Hadlock Brook watershed, with thicker soil and predominantly coniferous vegetation. Soils in both watersheds were primarily well drained. The fire had a significant impact on the Cadillac watershed, by raising the soil pH, altering the vegetation, and reducing carbon and Hg pools. Total Hg content was significantly higher (P > 0.05) in Hadlock soils (0.18 kg Hg ha-1) compared to Cadillac soils (0.13 kg Hg ha-1). Hadlock O horizon had an average Hg concentration of 134±48 ng Hg g-1 dry weight, compared to 103±23 ng Hg g-1 dry weight in Cadillac O horizon. Soil pH was significantly higher in all soil horizons at Cadillac compared to Hadlock soils. This difference was especially significant in the O horizon, where Cadillac soils had an average pH of 3.41±0.22 compared to Hadlock soils with an average pH of 2.99±0.13.To study the mobilization potential of Hg in the O horizons of the two watersheds, batch adsorption experiments were conducted, and the results were modeled using surface complexation modeling. The results of Hg adsorption experiments indicated that the dissolved Hg concentration was controlled by the dissolved organic carbon (DOC) concentration. The adsorption isotherms suggest that Hg is more mobile in the O horizon of the unburned Hadlock watershed because of higher solubility of organic carbon resulting in higher DOC concentrations in that watershed.Methylmercury concentrations, however, were consistently higher in the burned Cadillac O horizon (0.20±0.13 ng Hg g-1 dry weight) than in the unburned Hadlock O horizon (0.07±0.07 ng Hg g-1 dry weight). Similarly, Cadillac soils possessed a higher MeHg content (0.30 g MeHg ha-1) than Hadlock soils (0.16 g MeHg ha-1). The higher MeHg concentrations in Cadillac soils may reflect generally faster rates of microbial metabolism due to more rapid nutrient cycling and higher soil pH in the deciduous forest. In this research, we have shown that the amount of MeHg is not a function of the total pool of Hg in the watershed. Indeed, MeHg was inversely proportional to total Hg, suggesting that landscape factors such as soil pH, vegetation type, or land use history (e.g., fire) may be the determining factors for susceptibility to high Hg in biota.

Mercury sources and fate in the Gulf of Maine.

Most human exposure to mercury (Hg) in the United States is from consuming marine fish and shellfish. The Gulf of Maine is a complex marine ecosystem comprising twelve physioregions, including the Bay of Fundy, coastal shelf areas and deeper basins that contain highly productive fishing grounds. Here we review available data on spatial and temporal Hg trends to better understand the drivers of human and biological exposures. Atmospheric Hg deposition from U.S. and Canadian sources has declined since the mid-1990s in concert with emissions reductions and deposition from global sources has increased. Oceanographic circulation is the dominant source of total Hg inputs to the entire Gulf of Maine region (59%), followed by atmospheric deposition (28%), wastewater/industrial sources (8%) and rivers (5%). Resuspension of sediments increases MeHg inputs to overlying waters, raising concerns about benthic trawling activities in shelf regions. In the near coastal areas, elevated sediment and mussel Hg levels are co-located in urban embayments and near large historical point sources. Temporal patterns in sentinel species (mussels and birds) have in some cases declined in response to localized point source mercury reductions but overall Hg trends do not show consistent declines. For example, levels of Hg have either declined or remained stable in eggs from four seabird species collected in the Bay of Fundy since 1972. Quantitatively linking Hg exposures from fish harvested from the Gulf of Maine to human health risks is challenging at this time because no data are available on the geographic origin of seafood consumed by coastal residents. In addition, there is virtually no information on Hg levels in commercial species for offshore regions of the Gulf of Maine where some of the most productive fisheries are located. Both of these data gaps should be priorities for future research.

Photocatalytic degradation of 17α-ethinylestradiol (EE2) in the presence of TiO2-doped zeolite.

Current design limitations and ineffective remediation techniques in wastewater treatment plants have led to concerns about the prevalence of pharmaceutical and personal care products (PPCPs) in receiving waters. A novel photocatalyst, TiO2-doped low-silica X zeolite (TiO2-LSX), was used to study the degradation of the pharmaceutical compound, 17α-ethinylestradiol (EE2). The catalyst was synthesized and characterized using XRD, BET surface analysis, SEM-EDAX, and ICP-OES. The effects of different UV light intensities, initial EE2 concentrations, and catalyst dosages on the EE2 removal efficiency were studied. A higher EE2 removal efficiency was attained with UV-TiO2-LSX when compared with UV-TiO2 or UV alone. The EE2 degradation process followed pseudo-first-order kinetics. A comprehensive empirical model was developed to describe the EE2 degradation kinetics under different conditions using multiple linear regression analysis. The EE2 degradation mechanism was proposed based on molecular calculations, identification of photoproducts using HPLC-MS/MS, and reactive species quenching experiments; the results showed that oxidative degradation pathways initiated by hydroxyl radicals were predominant. This novel TiO2-doped zeolite system provides a promising application for the UV disinfection process in wastewater treatment plants.

Sediment geochemistry of Al, Fe, and P for two historically acidic, oligotrophic Maine lakes.

Phosphorus (P) may be liberated from lake sediments by reductive dissolution of Fe(OH)(3(S)) during periods of hypolimnetic anoxia. P, however, remains adsorbed to Al(OH)(3(S)) regardless of redox conditions. During chronic or episodic acidification of a catchment, ionic Al is mobilized from soils to receiving waters. A fraction of the mobilized Al may precipitate as a consequence of higher pH of the receiving waters. We hypothesized that phosphorus retention in lake sediments is directly related to the magnitude of Al loading in response to low pH in the watershed. We studied cores representing over 200 years of sediment accumulation in historically acidic Mud Pond and Little Long Pond in eastern Maine, USA. Sequential chemical extractions of sediment were used to assess the history of Al, Fe, and P interactions. Mud Pond is a first-order pond with a pH of approximately 4.7, having acidified slightly in response to anthropogenic acidification from approximately 1930. The inlet stream to Mud Pond has dissolved Al concentrations often exceeding 500 microg/L, of which more than half is organically-bound. Mud Pond drains into Little Long Pond, a second-order pond with a historical pH of <6, and which has shown little pH or alkalinity response to increases or decreases in atmospheric SO(4)(2-) input. Sequential extractions show that Al and P are predominantly in the 0.1 M NaOH-extractable fraction in the sediments from both ponds throughout the cores. The concentration of the likely biogenic and non-reactive P within the NaOH fraction increases up core from <30% to approximately 60%. Extractable Fe (<20% of extractable Al) is mainly in the 0.1 M NaOH-extractable fraction, except for the top few cm, which are predominantly in the bicarbonate-dithionite reducible fraction. Accumulation rates of sediment, Al, Fe, and P in both ponds have increased in the last 50-60 yr, but fractions remain in the same proportion. Throughout both sediment cores the molar ratio of specific Al:P fractions greatly exceeds 25, and molar ratio of specific Al:Fe fractions greatly exceeds 3, the thresholds proposed by Kopácek et al. [Kopácek J, Borovec J, Hejzlar J, Ulrich K-U, Norton SA, Amirbahman A. Aluminum control of phosphorus sorption by lake sediments. Environ Sci Technol 2005; 39: 8784-89.] for P release during anoxia. The data illustrate a continuous association of P with Al in both ponds during the last two centuries, likely due to the persistent natural acidity of the catchments.

Kinetics and mechanism of ligand-promoted decomposition of the Keggin Al13 polymer

The effect of five low molecular weight organic acids (oxalate, malonate, salicylate, phthalate and benzoate) on the decomposition kinetics of the Al13 polymer was studied in acidic aqueous solutions using a flow-through reactor that was operated under steady-state conditions. The results showed that those ligands that can form bidentate complexes with “surface” octahedral Al(III) centers are able to decompose Al13. Decomposition rates increased with increasing proton and ligand concentrations in the pH range studied (2.0 < pH < 4.8). Modeling of the decomposition process indicated the existence of two independent and parallel proton- and ligand-promoted pathways. The former pathway has been studied previously. We propose that the Al13-ligand complex (Al13L5+) is the precursor to the ligand-promoted decomposition. The rate of decomposition can be described as first-order with respect to the where the apparent ligand-promoted decomposition rate coefficient (kLa) generally has a first- and a second-order dependence on the proton concentration as kLa=kL1[H+]+kL2[H+]2 For oxalate at the pH range studied, second-order dependence on [H+] was negligible, possibly because of the ligand’s strong acidic character. At pH > 4, equimolar concentrations of the bidentate ligands enhanced the kinetics of Al13 decomposition by factors of up to 20 in comparison to proton-promoted decomposition in ligand-free solutions. The most distinct impact was observed for oxalate and phthalate followed by malonate. The monodentate ligand benzoate had no influence on the half-life of Al13. In contrast to the effects of ligands on the dissolution kinetics of solid δ-Al2O3, where salicylate is a powerful promoter, the kinetics of Al13 decomposition is enhanced only very little by salicylate. This difference in reactivity of solid aluminum oxide and the dissolved Al13 polymer towards the investigated bidentate ligands can be attributed to the different coordination geometry of the surface Al(III) centers in the two aluminum compounds. Based upon the order of reactivity of the ligands used in this study, we propose that the rate-determining step in the ligand-promoted decomposition of Al13 is formation of a “surface” bidentate complex.

Estimating pesticide sampling rates by the polar organic chemical integrative sampler (POCIS) in the presence of natural organic matter and varying hydrodynamic conditions

The polar organic chemical integrative sampler (POCIS) was calibrated to monitor pesticides in water under controlled laboratory conditions. The effect of natural organic matter (NOM) on the sampling rates (R(s)) was evaluated in microcosms containing <0.1-5 mg L(-1) of total organic carbon (TOC). The effect of hydrodynamics was studied by comparing R(s) values measured in stirred (SBE) and quiescent (QBE) batch experiments and a flow-through system (FTS). The level of NOM in the water used in these experiments had no effect on the magnitude of the pesticide sampling rates (p > 0.05). However, flow velocity and turbulence significantly increased the sampling rates of the pesticides in the FTS and SBE compared to the QBE (p < 0.001). The calibration data generated can be used to derive pesticide concentrations in water from POCIS deployed in stagnant and turbulent environmental systems without correction for NOM.

Mercury bioaccumulation in green frog (Rana clamitans) and bullfrog (Rana catesbeiana) tadpoles from Acadia National Park, Maine, USA

Mercury contamination in the northeastern United States, including Acadia National Park (ANP; ME, USA), is well documented and continues to be a public health issue of concern. Mercury contamination of wild amphibians has received little attention, however, despite reports of worldwide population declines. Here, we report total Hg and methyl Hg (MeHg) concentrations for water, sediment, and green frog (Rana clamitans) and bullfrog (Rana catesbeiana) tadpoles (age, approximately one year) from ANP. Total Hg concentrations (mean+/-standard error) in green frog and bullfrog tadpoles were 25.1+/-1.5 and 19.1+/-0.8 ng/g wet weight, respectively. Mean total Hg was highest for green frog tadpoles sampled from the Schooner Head site (ANP, Bar Harbor, ME, USA), a small, semipermanent beaver pond where Ranavirus was detected during the summer of 2003 sampling period. Methyl Hg comprised 7.6 to 40% of the total Hg in tadpole tissue (wet-wt basis), and mean total Hg levels in tadpoles were significantly different among pond sites (n = 9). Total Hg in pond water was a significant predictor of tadpole total Hg levels. Dissolved organic carbon was a significant predictor of both total Hg and MeHg in water, and total Hg in water also was strongly correlated with MeHg in water. Of the nine pond ecosystems sampled at ANP 44% had a methylation efficiency (water MeHg to total Hg ratio) of greater than 10%, and 33% had total Hg levels in sediment that were approximately equal to or greater than the established threshold level effect concentration for freshwater sediments (0.174 mg/kg dry wt). Our data indicate that wetland food webs in ANP likely are susceptible to high levels of total Hg bioaccumulation and that methylation dynamics appear to be influenced by local abiotic and biotic factors, including disturbances by beavers and in situ water chemistry patterns. These findings may be important to National Park Service resource managers, especially considering the class I airshed status of ANP and the strong potential for negative effects to aquatic ecosystem structure and function from Hg pollution.