Factors diminishing the effectiveness of phosphorus loading from municipal effluent: critical information for TMDL analyses

Factors that diminish the effectiveness of phosphorus inputs from a municipal wastewater treatment facility (Metro) in contributing to phosphorus levels and its availability to support algae growth in a culturally eutrophic urban lake (Onondaga Lake, NY) were characterized and quantified. These factors included the bioavailability and settling characteristics of particulate phosphorus from this effluent, the dominant form (70%) of phosphorus in this input, and the plunging of the discharge to stratified layers in the lake. Supporting studies included: (1) chemical and morphometric characterization of the phosphorus-enriched particles of this effluent, compared to particle populations of the tributaries and lake, with an individual particle analysis technique; (2) conduct of algal bioavailability assays of the particulate phosphorus of the effluent; (3) conduct of multiple size class settling velocity measurements on effluent particles; and (4) determinations of the propensity of the discharge to plunge, and documentation of plunging through three-dimensional monitoring of a tracer adjoining the outfall. All of these diminishing effects were found to be operative for the Metro effluent in Onondaga Lake and will be integrated into a forthcoming phosphorus "total maximum daily load" analysis for the lake, through appropriate representation in a supporting mechanistic water quality model. The particulate phosphorus in the effluent was associated entirely with Fe-rich particles formed in the phosphorus treatment process. These particles did not contribute to concentrations in pelagic portions of the lake, due to local deposition associated with their large size. Moreover, this particulate phosphorus was found to be nearly entirely unavailable to support algae growth. While substantial differences are to be expected for various inputs, the effective loading concept and the approaches adopted here to assess the diminishing factors are broadly applicable.     

Energy supplies and future engines for land, sea, and air

The years 2012 and beyond seem likely to record major changes in energy use and power generation. The Japanese tsunami has resulted in large countries either scaling back or abolishing the future use of nuclear energy. The discovery of what seems like vast amounts of economically deliverable natural gas has many forecasting a rapid switch from coal- to gas-fired generating plants. On the other hand, environmentalists have strong objections to the production of natural gas and of petroleum by hydraulic fracturing from shale, or by extraction of heavy oil. They believe that global warming from the use of fossil fuels is now established beyond question. There has been rapid progress in the development of alternative energy supplies, particularly from on-shore and off-shore wind. Progress toward a viable future energy mix has been slowed by a U.S. energy policy that seems to many to be driven by politics. The author will review the history of power and energy to put all of the above in context and will look at possible future developments. He will propose what he believes to be an idealized energy policy that could result in an optimum system that would be arrived at democratically.     

Copper kinetics and internal distribution in the marbled crayfish (Procambarus sp.)

Metal pollution e.g. copper, in water bodies occurs worldwide. Although copper is an essential trace metal, at certain levels it is still considered as pollutant. The aim of this study was to investigate the effect of exposure concentration on copper bioaccumulation in marbled crayfish (Procambarus sp.) by determining uptake and elimination kinetics. Crayfish were exposed to sub-lethal copper concentrations (average measured concentrations of 0.031 and 0.38 mg Cu L⁻¹) for 14 d and transferred to copper-free water for another 14 d. At different time points during the uptake and elimination phases copper concentrations were measured in five organs (exoskeleton, gills, muscle, ovaries and hepatopancreas). At 0.031 mg Cu L⁻¹, copper levels in the crayfish organs were not significantly increased compared to the control animals, suggesting effective regulation. Exposure to 0.38 mg Cu L⁻¹ did lead to not significantly increased copper levels in muscles and ovaries, while the gills and exoskeleton, which are in direct contact with the water, showed significantly higher copper concentrations. In these four organs, copper showed fast uptake kinetics with equilibrium reached within 10 d of exposure. Copper accumulation was highest in the hepatopancreas; uptake in this storage organ steadily increased with time and did not reach equilibrium within the 14-d exposure period. Copper accumulation levels in the marbled crayfish found in this study were hepatopancreas > gills > exoskeleton > muscle.     

Predator cues and an herbicide affect activity and emigration in an agrobiont wolf spider

Animals use chemical cues for signaling between species. However, anthropogenic chemicals might interrupt this natural chemical information flow, with potential impacts on predator-prey interactions. Our goal was to explore how Buccaneer® Plus, a common herbicide similar to Round-up® (active ingredient glyphosate), affected the interactions between intraguild predators. The wolf spider Pardosa milvina (Hentz, 1844) is numerically dominant in agricultural systems across the eastern United States, and often falls prey to or competes with the larger wolf spider, Hogna helluo (Walckenaer, 1837) and/or the carabid beetle, Scarites quadriceps (Chaudoir, 1843). We tested the effects of chemical cues from these intraguild predators and exposure to herbicide on the activity, emigration, and survival of P. milvina using a full-factorial laboratory experiment. Both predator cues and herbicide led to a decrease in movement by P. milvina. However, although H. helluo cues alone decreased movement, S. quadriceps cues only decreased movement when combined with herbicide. These results indicate that predation risk and herbicide application likely interact in complex ways to affect the movement of a major arthropod predator in agricultural systems, and thus may have complex effects on the food web.     

Modeling urban films using a dynamic multimedia fugacity model

A thin film coats impervious urban surfaces that can act as a source or sink of organic pollutants to the greater environment. We review recent developments in the understanding of film and film-associated pollutant behavior and incorporate them into an unsteady-state version of the fugacity based Multimedia Urban Model (MUM), focusing on detailed considerations of surface film dynamics. The model is used to explore the conditions under which these atmospherically-derived films act as a temporary source of chemicals to the air and/or storm water. Assuming film growth of 2.1 nm d⁻¹ (Wu et al., 2008a), PCB congeners 28 and 180 reach air-film equilibrium within hours and days, respectively. The model results suggest that the film acts as a temporary sink of chemicals from air during dry and cool weather, as a source to air in warmer weather, and as a source to storm water and soil during rain events. Using the downtown area of the City of Toronto Canada, as a case study, the model estimates that nearly 1 g d⁻¹ of ∑₅PCBs are transferred from air to film to storm water.     

Interference with xenobiotic metabolic activity by the commonly used vehicle solvents dimethylsulfoxide and methanol in zebrafish (Danio rerio) larvae but not Daphnia magna

Organic solvents, such as dimethylsulfoxide (DMSO) and methanol are widely used as vehicles to solubilise lipophilic test compounds in toxicity testing. However, the effects of such solvents upon innate detoxification processes in aquatic organisms are poorly understood. This study assessed the effect of solvent exposure upon cytochrome P450 (CYP)-mediated xenobiotic metabolism in Daphnia magna and zebrafish larvae (4 d post fertilisation). Adult D. magna were demonstrated to have a low, but detectable, metabolism of ethoxyresorufin in vivo and this activity was not modulated by pre-exposure to DMSO or methanol (24 h, up to 0.1% and 0.05% v/v, respectively). In contrast, the metabolism of ethoxyresorufin in zebrafish larvae was significantly reduced by both solvents (0.1% and 0.05% v/v, respectively) after 24 h of exposure. In zebrafish, these observed decreases in activity towards ethoxyresorufin were accompanied by decreased expression of a variety of genes coding for drug metabolising enzymes (corresponding to CYP1, CYP2, CYP3 and UDP-glucuronyl transferase [UGT] family enzymes), measured by quantitative PCR. Reduction of gene expression and CYP1 enzyme activities by methanol (0.05% v/v) in zebrafish larvae was partially reversed by co-exposure with Aroclor 1254 (100 μg L⁻¹). Overall this study suggests that relatively low concentrations of organic solvents can impact upon the biotransformation of certain xenobiotics in zebrafish larvae, and that this warrants consideration when assessing compounds for metabolism and toxicity in this species.     

Influence of Suwannee River humic acid on particle properties and toxicity of silver nanoparticles

Adsorption of natural organic matter (NOM) on nanoparticles can have dramatic impacts on particle dispersion resulting in altered fate and transport as well as bioavailability and toxicity. In this study, the adsorption of Suwannee River humic acid (SRHA) on silver nanoparticles (nano-Ag) was determined and showed a Langmuir adsorption at pH 7 with an adsorption maximum of 28.6 mg g⁻¹ nano-Ag. It was also revealed that addition of <10 mg L⁻¹ total organic carbon (TOC) increased the total Ag content suspended in the aquatic system, likely due to increased dispersion. Total silver content decreased with concentrations of NOM greater than 10 mg TOC L⁻¹ indicating an increase in nanoparticle agglomeration and settling above this concentration. However, SRHA did not have any significant effect on the equilibrium concentration of ionic Ag dissolved in solution. Exposure of Daphnia to nano-Ag particles (50 μg L⁻¹ and pH 7) produced a linear decrease in toxicity with increasing NOM. These results clearly indicate the importance of water chemistry on the fate and toxicity of nanoparticulates.     

Characterization of silver release from commercially available functional (nano)textiles

Silver, both in the nano as well as in other forms, is used in many applications including antimicrobial textiles. Washing of such textiles has already been identified as an important process that results in the release of silver into wastewater. This study thus investigated the release of silver from eight different commercially available silver-textiles during a washing and rinsing cycle. The silver released was size-fractionated and characterized using electron microscopy. In addition, the antimicrobial functionality of the textiles was tested before and after washing. Three of the textiles contained nanosized silver (labeled or confirmed by manufacturers’ information), another used a metallic silver wire and four contained silver in undeclared form. The initial silver content of the textiles was between 1.5 and 2925 mg Ag/kg. Only four of the investigated textiles leached detectable amounts of silver, of which 34-80% was in the form of particles larger than 450 nm. Microscopic analysis of the particles released in the washing solutions identified Ti/Si-AgCl nanocomposites, AgCl nanoparticles, large AgCl particles, nanosilver sulfide and metallic nano-Ag, respectively. The nanoparticles were mainly found in highly agglomerated form. The identified nanotextiles showed the highest antimicrobial activity, whereas some of the other textiles, e.g. the one with a silver wire and the one with the lowest silver content, did not reduce the growth of bacteria at all. The results show that different silver textiles release different forms of silver during washing and that among the textiles investigated AgCl was the most frequently observed chemical form in the washwater.     

Chromium speciation in river sediment pore water contaminated by tannery effluent

Cr(VI) is far more soluble and toxic than Cr(III). Sediment pore water was investigated in a river adjacent to the property of a large former tannery, into which Cr-contaminated effluent was discharged over a 55-year period, and where extremely high Cr concentrations have been found in the sediments. Dialysis cells, or peepers, were used to generate depth profiles of Cr concentration in sediment pore water. Samples were analyzed for total Cr using inductively coupled plasma-mass spectrometry (ICP-MS) and for Cr species using high performance liquid chromatography (HPLC)-ICP-MS. The results show an absence of Cr(VI) in all samples. Furthermore, incomplete recovery of Cr(VI) added to the samples collected at the locations with highest sediment Cr concentrations indicate strong reducing conditions at those locations, which are not conducive to the presence of Cr(VI).     

Nonideal transport of contaminants in heterogeneous porous media: 10. Impact of co-solutes on sorption by porous media with low organic-carbon contents

The impact of co-solutes on sorption of tetrachloroethene (PCE) by two porous media with low organic-carbon contents was examined by conducting batch experiments. The two media (Borden and Eustis) have similar physical properties, but significantly different organic-carbon (OC) contents. Sorption of PCE was nonlinear for both media, and well-described by the Freundlich equation. For the Borden aquifer material (OC = 0.03%), the isotherms measured with a suite of co-solutes present (1,2-dichlorobenzene, bromoform, carbon tetrachloride, and hexachloroethane) were identical to the isotherms measured for PCE alone. These results indicate that there was no measurable impact of the co-solutes on PCE sorption for this system. In contrast to the Borden results, there was a measurable reduction in sorption of PCE by the Eustis soil (OC = 0.38%) in the presence of the co-solutes. The organic-carbon fractions of both media contain hard-carbon components, which have been associated with the manifestation of nonideal sorption phenomena. The disparity in results observed for the two media may relate to relative differences in the magnitude and geochemical nature of these hard-carbon components.