Spatial and temporal variability of mercury in Upper and Lower Red Lake Walleye.

Mercury is a global pollutant that is released into our environment by natural and anthropogenic processes resulting in extensive studies of mercury cycling in aquatic ecosystems, and the issuance of human-health-based fish-consumption advisories. We examined total mercury concentrations in Walleye Sander vitreus from Upper and Lower Red Lakes, located in north central Minnesota, between 2019 and 2020. Sampled Walleye (n = 265) ranged from 158 to 610 mm in total length from an age range of young-of-the year to 16 years. Mercury concentrations within the Walleye ranged from 0.030 mg/kg to 0.564 mg/kg (x̄ = 0.179 ± 0.105 mg/kg; x̄ = mean ± sd, all fish-mercury concentrations expressed on wet-weight basis). The best supported model for predicting mercury concentrations in Red Lake Walleye included the independent variables: length, age, sex, and lake basin. This model indicated that there was a significant difference in mercury concentrations between Upper and Lower Red Lake (x̄ = 0.215 ± 0.117 and 0.144 ± 0.077 mg/kg, respectively), and also suggests that individuals who rely on fish for subsistence should target Walleye that are ≤ 400 mm from Lower Red Lake. Observed differences in mercury concentrations could be linked to wetland area influences, fish growth rates, and physicochemical parameters between the two basins. Given that our results illustrated a significant difference in fish-mercury concentrations between basins, future pollutant monitoring efforts should treat Upper and Lower Red Lake as separate lakes and not assume that data from one basin can apply to the other.

Biological control of biofilms on membranes by metazoans.

Traditionally, chemical and physical methods have been used to control biofouling on membranes by inactivating and removing the biofouling layer. Alternatively, the permeability can be increased using biological methods while accepting the presence of the biofouling layer. We have investigated two different types of metazoans for this purpose, the oligochaete Aelosoma hemprichi and the nematode Plectus aquatilis. The addition of these grazing metazoans in biofilm-controlled membrane systems resulted in a flux increase of 50% in presence of the oligochaetes (Aelosoma hemprichi), and a flux increase of 119-164% in presence of the nematodes (Plectus aquatilis) in comparison to the control system operated without metazoans. The change in flux resulted from (1) a change in the biofilm structure, from a homogeneous, cake-like biofilm to a more heterogeneous, porous structure and (2) a significant reduction in the thickness of the basal layer. Pyrosequencing data showed that due to the addition of the predators, also the community composition of the biofilm in terms of protists and bacteria was strongly affected. The results have implications for a range of membrane processes, including ultrafiltration for potable water production, membrane bioreactors and reverse osmosis.

Effect of TiO2 nanoparticles and UV radiation on extracellular enzyme activity of intact heterotrophic biofilms.

When introduced into the aquatic environment, TiO2 NP are likely to settle from the water column, which results in increased exposure of benthic communities. Here, we show that the activity of two extracellular enzymes of intact heterotrophic biofilms, ß-glucosidase (carbon-cycling) and l-leucin aminopeptidase (nitrogen-cycling), was reduced following exposure to surface functionalized TiO2 NP and UV radiation, depending on the particles' coating. This reduction was partially linked to ROS production. Alkaline phosphatase (phosphorus-cycling) activity was not affected, however in contrast, an alkaline phosphatase isolated from E. coli was strongly inhibited at lower concentrations of TiO2 NP than the intact biofilms. These results indicate that enzymes present in the biofilm matrix are partly protected against exposure to TiO2 NP and UV radiation. Impairment of extracellular enzymes which mediate the uptake of nutrients from water may affect ecosystem function.

Chemical Aspects of Nanoparticle Ecotoxicology.

Nanoecotoxicology strives to understand the processes and mechanisms by which engineered nanoparticles (ENP) may exert toxic effects on aquatic organisms. Detailed knowledge of the chemical reactions of nanoparticles in the media and of their interactions with organisms is required to understand these effects. The processes of agglomeration of nanoparticles, of dissolution and release of toxic metal ions, and of production of reactive oxygen species (ROS) are considered in this article. Important questions concern the role of uptake of nanoparticles in various organisms, in contrast to uptake of ions released from nanoparticles and to nanoparticle attachment to organism surfaces. These interactions are illustrated for effects of silver nanoparticles (AgNP), cerium oxide (CeO2 NP) and titanium dioxide (TiO2 NP), on aquatic organisms, including algae, biofilms, fish cells and fish embryos.

Fullerene nanoparticles exhibit greater retention in freshwater sediment than in model porous media.

Increasing production and use of fullerene-based nanomaterials underscore the need to determine their mobility in environmental transport pathways and potential ecological exposures. This study investigated the transport of two fullerenes (i.e., aqu/C(60) and water-soluble C(60) pyrrolidine tris-acid [C(60) PTA]) in columns packed with model porous media (Iota quartz and Ottawa sand) and a sediment from Call's creek under saturated and unsaturated steady-state flows. The fullerenes had the least retention in Iota quartz, and the greatest retention in the sediment at near neutral pH, correlating with the degree of grain surface chemical heterogeneity (e.g., amorphous Al hydroxides concentration increasing in the order of Iota quartz

Temporal changes in Aqu/C60 physical-chemical, deposition, and transport characteristics in aqueous systems.

Little is known about how temporal changes in the physical-chemical properties of C60 aggregates formed in aqueous systems (termed aqu/C60) can impact transport pathways contributing to ecological exposures. In this study three aqu/C60 suspensions of short-term (100 days), intermediate-term (300 days), and long-term (1000 days) water exposure were first characterized for particle size distribution, water/toluene phase distribution, and surface chemistry. Then, aqu/C60 deposition to a model silica surface and transport in porous media were studied by quartz crystal microbalance (QCM) and saturated sand columns. As suspension time increased, aqu/C60 particle size shifted to a larger size range as determined by asymmetric flow field-flow fractionation (AF4) and the aqu/C60 distribution to toluene was reduced, likely due to surface polarization as revealed by nuclear magnetic resonance (NMR) and UV-visible spectroscopy of the aqu/C60 suspensions. Additionally, the deposition to silica surfaces in both QCM and column studies decreased with increased water exposure time. Although a small increase in aqu/C60 aggregate size with time may partially explain the greater transport of the long-term aqu/C60 because of the decreased collector efficiency for larger submicrometer particles, the polarization of the aqu/C60 (thus a more hydrophilic surface) revealed by the toluene/water phase distribution and confirmed by NMR, is considered the determining factor.

Changes in agglomeration of fullerenes during ingestion and excretion in Thamnocephalus platyurus.

The crustacean Thamnocephalus platyurus was exposed to aqueous suspensions of fullerenes C(60) and C(70) . Aqueous fullerene suspensions were formed by stirring C(60) and C(70) as received from a commercial vendor in deionized water (termed aqu/C(60) and aqu/C(70) ) for approximately 100 d. The Z-average (mean hydrodynamic) diameters of aqu/C(60) and aqu/C(70) aggregates as measured by dynamic light scattering were 517 ± 21 nm and 656 ± 39 nm (mean ± 95% confidence limit), respectively. Exposure of T. platyurus to fullerene suspensions resulted in the formation of dark masses in the digestive track visible under a stereo microscope (×40 magnification). Fullerene ingestion over 1 h of exposure was quantitatively determined after extraction and analysis by high-performance liquid chromatography-mass spectrometry (HPLC-MS). One-hour exposures (at 3 mg/L and 6 mg/L) resulted in aqu/C(60) burdens of 2.7 ± 0.4 µg/mg and 6.8 ± 1.5 µg/mg wet weight, respectively. Thin-section transmission electron microscopy (TEM) images of aqu/C(60) -exposed T. platyurus showed the formation in the gut of fullerene agglomerates (5-10 µm) that were an order of magnitude larger than the suspended fullerene agglomerates. Upon excretion, the observed fullerene agglomerates were in the 10- to 70-µm size range and settled to the bottom of the incubation wells. In contrast to the control polystyrene microspheres, which dispersed after depuration, the aqu/C(60) agglomerates (greater than two orders of magnitude larger than the suspended fullerenes) remained agglomerated for up to six months. When exposed to fullerenes, T. platyurus shows the potential to influence agglomerate size and may facilitate movement of these nanoparticles from the water column into sediment.

Effects of humic acid and sunlight on the generation and aggregation state of aqu/C60 nanoparticles.

Aqueous suspensions of nanoscale C(60) aggregates (aqu/C(60)) were produced by stirring in water with Suwanee River Humic Acid (humic acid) and water from Call's Creek, a small stream near Athens, GA. Time course experiments were conducted to determine the effects of sunlight and solution chemistry on the mass of aqu/C(60) suspended, nanoparticle size, and ζ potential. For all treatments, sunlight had the greatest effect on the mass of aqu/C(60) suspended. The sunlight-exposed Call's Creek samples exhibited the greatest increase in mass suspended with aqu/C(60) concentrations 17 times greater than those of the dark controls, followed by the humic acid treatments, 8.1 times, and deionized water, 3.4 times. Asymmetric flow field-flow fractionation indicated that aqu/C(60) nanoparticles in humic acid were the smallest and their mass was evenly distributed in the 120-300 nm hydrodynamic diameter (D(h)) size range, whereas aqu/C(60) nanoparticles in Call's Creek water were the largest and were evenly distributed in the size range of 200-300 nm D(h). Aqu/C(60) in deionized water and humic acid treatments exposed to sunlight exhibited a trend of increasingly negative ζ potentials as suspension time increased; however, this trend was not observed for the Call's Creek treatment.

Asymmetric flow field flow fractionation of aqueous C60 nanoparticles with size determination by dynamic light scattering and quantification by liquid chromatography atmospheric pressure photo-ionization mass spectrometry.

A size separation method was developed for aqueous C60 fullerene aggregates (aqu/C60) using asymmetric flow field flow fractionation (AF4) coupled to a dynamic light scattering detector in flow through mode. Surfactants, which are commonly used in AF4, were avoided as they may alter suspension characteristics. Aqu/C60 aggregates generated by sonication in deionized water ranged in size from 80 to 260 nm in hydrodynamic diameter (Dh) as determined by DLS in flow through mode, which was corroborated by analysis of fractions by DLS in batch mode and by TEM. The mass of C60 in each fraction was determined by LC-APPI-MS. Only 5.2+/-6.7% of the total aqu/C60 mass had Dh less than 80 nm, while 58+/-32% of the total aqu/C60 mass had Dh between 80 and 150 nm and 14+/-9.2% of the total aqu/C60 were between 150 and 260 nm in Dh. With the optimal fractionation parameters, 77+/-5.8% of the aqu/C60 mass eluted from the AF4 channel, indicating deposition on the AF4 membrane had occurred during fractionation; use of alternative membranes did not reduce deposition. Channel flow splitting increased detector response although channel split ratios greater than 80% of the channel flow led to decreased detector response. This is the first report on the use of AF4 for fractionating a colloidal suspension of aqu/C60.

Quantitative analysis of fullerene nanomaterials in environmental systems: a critical review.

The increasing production and use of fullerene nanomaterials has led to calls for more information regarding the potential impacts that releases of these materials may have on human and environmental health. Fullerene nanomaterials, which are comprised of both fullerenes and surface-functionalized fullerenes, are used in electronic, optic, medical, and cosmetic applications. Measuring fullerene nanomaterial concentrations in natural environments is difficult because they exhibit a duality of physical and chemical characteristics astheytransition from hydrophobic to polar forms upon exposure to water. In aqueous environments, this is expressed as their tendency to initially (i) self-assemble into aggregates of appreciable size and hydrophobicity, and subsequently (ii) interact with the surrounding water molecules and other chemical constituents in natural environments thereby acquiring negative surface charge. Fullerene nanomaterials may therefore deceive the application of any single analytical method that is applied with the assumption that fullerenes have but one defining characteristic (e.g., hydrophobicity). Our findings include the following: (1) Analytical procedures are needed to account for the potentially transitory nature of fullerenes in natural environments through the use of approaches that provide chemically explicit information including molecular weight and the number and identity of surface functional groups. (2) Sensitive and mass-selective detection, such as that offered by mass spectrometry when combined with optimized extraction procedures, offers the greatest potential to achieve this goal. (3) Significant improvements in analytical rigor would result from an increased availability of well characterized authentic standards, reference materials, and isotopically labeled internal standards. Finally, the benefits of quantitative and validated analytical methods for advancing the knowledge on fullerene occurrence, fate, and behavior are indicated.

Colloidal properties of aqueous fullerenes: isoelectric points and aggregation kinetics of C60 and C60 derivatives.

Aqueous colloidal suspensions of C60 (aqu/C60) and the C60 derivatives PCBM ([6,6]-phenyl C61-butyric acid methyl ester) and the corresponding butyl and octyl esters, PCBB and PCBO (aqu/PCB-R, where R is an alkyl group), were produced by stirring in double deionized water for 5 months. Kinetically stable fullerene aggregates were formed using this procedure that ranged in intensity-averaged hydrodynamic diameter (Dh) from 193 +/- 2 nm (95% C.L.) for aqu/C60 to 259 +/- 6 nm for aqu/PCBO. Measured zeta potentials (zeta) were < -50 mV, and the isoelectric points (p) were < 1.0 for all of the aqu/fullerenes. Time-resolved dynamic light scattering (TRDLS) was used to measure aqu/fullerene Dh change with time and as a function of background solution ionic strength. The critical coagulation concentration (CCC) values for the aqu/PCB-R fullerenes were significantly higher than that of aqu/C60, indicating that the phenyl alkyl ester moieties of the equ/PCB-R fullerenes were impeding the aggregation process.

Quantification of fullerenes by LC/ESI-MS and its application to in vivo toxicity assays.

With production and use of carbon nanoparticles increasing, it is imperative that the toxicity of these materials be determined; yet such testing requires specific and selective analytical methodologies that do not yet exist. Quantitative liquid-liquid extraction was coupled with liquid chromatography/electrospray ionization mass spectrometry for the quantitative determination of fullerenes from C60 to C98. Isotopically enriched, 13C60, was used as an internal standard. The method was applied to determine the loss of C60 from exposure water solution and uptake of C60 by embryonic zebrafish. The average recovery of C60 from zebrafish embryo extracts and 1% DMSO in aqueous-exposure solutions was 90 and 93%, respectively, and precision, as indicated by the relative standard deviation, was 2 and 7%, respectively. The method quantification limit was 0.40 microg/L and the detection limit was 0.02 microg/L. During the toxicological assay, loss of C60 due to sorption to test vials resulted in the reduction of exposure-solution concentrations over 6 h to less than 50% of the initial concentration. Time-course experiments indicated embryo uptake increased over course of the 12-h exposure. A lethal concentration that caused 50% mortality was determined to be 130 microg/L and was associated with a zebrafish embryo concentration, LD50, of 0.079 microg/g of embryo.

Quantitative determination of 1,4-dioxane and tetrahydrofuran in groundwater by solid phase extraction GC/MS/MS.

Groundwater contamination by cyclic ethers, 1,4-dioxane (dioxane), a probable human carcinogen, and tetrahydrofuran (THF), a co-contaminant at many chlorinated solvent release sites, are a growing concern. Cyclic ethers are readily transported in groundwater, yet little is known about their fate in environmental systems. High water solubility coupled with low Henry's law constants and octanol-water partition coefficients make their removal from groundwater problematic for both remedial and analytical purposes. A solid-phase extraction (SPE) method based on activated carbon disks was developed for the quantitative determination of dioxane and THF. The method requires 80 mL samples and a total of 1.2 mL of solvent (acetone). The number of steps is minimized due to the "in-vial" elution of the disks. Average recoveries for dioxane and THF were 98% and 95%, respectively, with precision, as indicated by the relative standard deviation of <2% to 6%. The method quantitation limits are 0.31 microg/L for dioxane and 3.1 microg/L for THF. The method was demonstrated by analyzing groundwater samples for dioxane and THF collected during a single sampling campaign at a TCA-impacted site. Dioxane concentrations and areal extent of dioxane in groundwater were greater than those of either TCA or THF.