Prioritizing research for trace pollutants and emerging contaminants in the freshwater environment

Organic chemicals have been detected at trace concentrations in the freshwater environment for decades. Though the term trace pollutant indicates low concentrations normally in the nanogram or microgram per liter range, many of these pollutants can exceed an acceptable daily intake (ADI) for humans. Trace pollutants referred to as emerging contaminants (ECs) have recently been detected in the freshwater environment and may have adverse human health effects. Analytical techniques continue to improve; therefore, the number and frequency of detections of ECs are increasing. It is difficult for regulators to restrict use of pollutants that are a human health hazard; scientists to improve treatment techniques for higher priority pollutants; and the public to modify consumption patterns due to the vast number of ECs and the breadth of literature on the occurrence, use, and toxicity. Hence, this paper examines literature containing occurrence and toxicity data for three broad classes of trace pollutants and ECs (industrials, pesticides, and pharmaceuticals and personal care products (PPCPs)), and assesses the relevance of 71 individual compounds. The evaluation indicates that widely used industrials (BPF) and PPCPs (AHTN, HHCB, ibuprofen, and estriol) occur frequently in samples from the freshwater environment but toxicity data were not available; thus, it is important to establish their ADI. Other widely used industrials (BDE-47, BDE-99) and pesticides (benomyl, carbendazim, aldrin, endrin, ethion, malathion, biphenthrin, and cypermethrin) have established ADI values but occurrence in the freshwater environment was not well documented. The highest priority pollutants for regulation and treatment should include industrials (PFOA, PFOS and DEHP), pesticides (diazinon, methoxychlor, and dieldrin), and PPCPs (EE2, carbamazepine, βE2, DEET, triclosan, acetaminophen, and E1) because they occur frequently in the freshwater environment and pose a human health hazard at environmental concentrations.     

Differential toxicity of silver and titanium dioxide nanoparticles on Drosophila melanogaster development, reproductive effort, and viability: size, coatings and antioxidants matter

Silver and titanium dioxide nanoparticles are known to induce oxidative stress in vitro and in vivo. Here we test if they impact development, mating success, and survivorship in Drosophila melanogaster, and if so, if these effects are reversible by antioxidants. Ingestion of nanotitanium dioxide during the larval stage of the life cycle showed no effects on development or survivorship, up to doses of 200 μg mL⁻¹. Conversely, ingestion of nanosilver had major dose, size, and coating-dependent effects on each of these aspects of life history. Each of these effects was partially or fully reversible by vitamin C. Larvae growing on nanosilver supplemented with vitamin C showed a greater than twofold increase in survivorship compared to flies reared on nanosilver alone, and a threefold increase in mating success. Vitamin C also rescued cuticular and pigmentation defects in nanosilver fed flies. Biochemical assays of superoxide dismutase and glutathione show these markers respond to nanotitanium dioxide and nanosilver induced oxidative stress, and this response is reduced by vitamin C. These results indicate that life history effects of nanosilver ingestion result from oxidative stress, and suggest antioxidants as a potential remediation for nanosilver toxicity. Conversely, the lack of nanotitanium dioxide life history toxicity shows that oxidative stress does not necessarily result in whole organism effects, and argues that nanoparticle toxicity needs to be examined at different levels of biological organization.     

The toxicology of climate change: Environmental contaminants in a warming world

Climate change induced by anthropogenic warming of the earth's atmosphere is a daunting problem. This review examines one of the consequences of climate change that has only recently attracted attention: namely, the effects of climate change on the environmental distribution and toxicity of chemical pollutants. A review was undertaken of the scientific literature (original research articles, reviews, government and intergovernmental reports) focusing on the interactions of toxicants with the environmental parameters, temperature, precipitation, and salinity, as altered by climate change. Three broad classes of chemical toxicants of global significance were the focus: air pollutants, persistent organic pollutants (POPs), including some organochlorine pesticides, and other classes of pesticides. Generally, increases in temperature will enhance the toxicity of contaminants and increase concentrations of tropospheric ozone regionally, but will also likely increase rates of chemical degradation. While further research is needed, climate change coupled with air pollutant exposures may have potentially serious adverse consequences for human health in urban and polluted regions. Climate change producing alterations in: food webs, lipid dynamics, ice and snow melt, and organic carbon cycling could result in increased POP levels in water, soil, and biota. There is also compelling evidence that increasing temperatures could be deleterious to pollutant-exposed wildlife. For example, elevated water temperatures may alter the biotransformation of contaminants to more bioactive metabolites and impair homeostasis. The complex interactions between climate change and pollutants may be particularly problematic for species living at the edge of their physiological tolerance range where acclimation capacity may be limited. In addition to temperature increases, regional precipitation patterns are projected to be altered with climate change. Regions subject to decreases in precipitation may experience enhanced volatilization of POPs and pesticides to the atmosphere. Reduced precipitation will also increase air pollution in urbanized regions resulting in negative health effects, which may be exacerbated by temperature increases. Regions subject to increased precipitation will have lower levels of air pollution, but will likely experience enhanced surface deposition of airborne POPs and increased run-off of pesticides. Moreover, increases in the intensity and frequency of storm events linked to climate change could lead to more severe episodes of chemical contamination of water bodies and surrounding watersheds. Changes in salinity may affect aquatic organisms as an independent stressor as well as by altering the bioavailability and in some instances increasing the toxicity of chemicals. A paramount issue will be to identify species and populations especially vulnerable to climate–pollutant interactions, in the context of the many other physical, chemical, and biological stressors that will be altered with climate change. Moreover, it will be important to predict tipping points that might trigger or accelerate synergistic interactions between climate change and contaminant exposures.     

Parents adjust care in response to weather conditions and egg dehydration in a Neotropical glassfrog

Parental hydration of terrestrially developing eggs has evolved repeatedly among frogs and is thought to buffer embryos from environmental variation. While many anurans offer relevant opportunities to study parental care, research on how parents respond to environmental variation and offspring conditions are lacking. In this study, we investigated the interrelationships of weather, embryo hydration demands, and parental provisioning in a wild population of the glassfrog Hyalinobatrachium (‘Centrolenella’) fleischmanni in Oaxaca, Mexico. We determined whether males modify parental behavior in response to changes in weather conditions that effect embryo dehydration, how variation in both weather and parental hydration affect egg water balance and embryonic mortality, and whether parental provisioning is related to the hydration levels of egg clutches. We found that male H. fleischmanni compensate for environmental variation in offspring conditions by adjusting the frequency of parental care in response to both weather and egg dehydration. Using a male removal experiment, we examined the function of paternal care and made comparisons with previous research, finding that both the adaptive value of parental care and flexibility in parental behavior are impacted by spatial and temporal conditions. We present observations that indicate a direct conflict between providing parental care and multiple matings. In summary, this research demonstrates that the variable frequency of paternal care in H. fleischmanni is a response to the fluctuating nature of the climate and resulting hydration requirements of embryos in combination with the allocation of effort to parental care versus mating activity.     

BATCH REACTOR UNVEGETATED WETLAND PERFORMANCE IN TREATING DAIRY WASTEWATER1

ABSTRACT: Wetlands that treat holding pond effluent can be designed to utilize the pond storage capacity to allow flexibility in system management. Management of a wetland as a sequencing batch reactor can simplify operation and control detention times, but little performance data on such systems are available. The objective of this study was to evaluate the batch reactor wetland concept by quantifying removal of chemical oxygen demand (COD), total suspended sediments (TSS), total nitrogen (TN), ammonium (NH₄), nitrate (NO₃), total phosphorus (TP), and orthophosphate (PO₄) and by assessing the suitability of first‐order kinetics. Weekly samples were collected following batch loadings of wetland cells with high concentration or low concentration dairy holding pond wastewater during both fall and spring seasons. During three‐week batch periods without plants, overall mass removal averaged 54 percent for COD, 58 percent for TSS, 90 percent for TN, 72 percent for NH₄, ‐54 percent for NO₃, 38 percent for TP, and ‐8 percent for PO₄. Best fit, first‐order kinetic rate constant (k) and background concentration (C*) for COD varied by season, with k = 0.024/d and C*= 0 mg/l in fall and k = 0.056/d and C*= 200 mg/l in spring. Ammonium exhibited a consistent C*= 0 mg/l but had variable rate constants of k = 0.121/d for low concentration treatments and k = 0.079/d for high concentration treatments. Using first‐order kinetics was also appropriate for TN, with k = 0.061/d and C*= 0 mg/l for all loadings and seasons, but was not consistently appropriate for TP or PO₄. These results support the use of first‐order kinetics to describe treatment in batch reactor wastewater treatment wetlands without vegetation, perhaps during the establishment phase or in open water zones of vegetated wetlands. Further work is needed to assess the effects of vegetation.     

Grass‐Shrub Riparian Buffer Removal of Sediment,Phosphorus, and Nitrogen From Simulated Runoff1

Abstract: Riparian buffer forests and vegetative filter strips are widely recommended for improving surface water quality, but grass‐shrub riparian buffer system (RBSs) are less well studied. The objective of this study was to assess the influence of buffer width and vegetation type on the key processes and overall reductions of total suspended solids (TSS), phosphorus (P), and nitrogen (N) from simulated runoff passed through established (7‐year old) RBSs. Nine 1‐m RBS plots, with three replicates of three vegetation types (all natural selection grasses, two‐segment buffer with native grasses and plum shrub, and two‐segment buffer with natural selection grasses and plum shrub) and widths ranging from 8.3 to 16.1 m, received simulated runoff having 4,433 mg/l TSS from on‐site soil, 1.6 mg/l total P, and 20 mg/l total N. Flow‐weighted samples were collected by using Runoff Sampling System (ROSS) units. The buffers were very efficient in removal of sediments, N, and P, with removal efficiencies strongly linked to infiltration. Mass and concentration reductions averaged 99.7% and 97.9% for TSS, 91.8% and 42.9% for total P, and 92.1% and 44.4% for total N. Infiltration alone could account for >75% of TSS removal, >90% of total P removal, and >90% of total N removal. Vegetation type induced significant differences in removal of TSS, total P, and total N. These results demonstrate that adequately designed and implemented grass‐shrub buffers with widths of only 8 m provide for water quality improvement, particularly if adequate infiltration is achieved.     

Interaction of carbonaceous nanomaterials with wastewater biomass

Increasing production and use of carbonaceous nanomaterials (NMs) will increase their release to the sewer system and to municipal wastewater treatment plants. There is little quantitative knowledge on the removal of multi-walled carbon nanotubes (MWCNTs), graphene oxide (GO), or few-layer graphene (FLG) from wastewater into the wastewater biomass. As such, we investigated the quantification of GO and MWCNTs by UV-Vis spectrophotometry, and FLG using programmable thermal analysis (PTA), respectively. We further explored the removal of pristine and oxidized MWCNTs (O-MWCNTs), GO, and FLG in a biomass suspension. At least 96% of pristine and O-MWCNTs were removed from the water phase through aggregation and 30-min settling in presence or absence of biomass with an initial MWCNT concentration of 25 mg·L⁻¹. Only 65% of GO was removed with biomass concentration at or above 1,000 mg·L⁻¹ as total suspended solids (TSS) with the initial GO concentration of 25 mg·L⁻¹. As UV-Vis spectrophotometry does not work well on quantification of FLG, we studied the removal of FLG at a lower biomass concentration (50 mg TSS·L⁻¹) using PTA, which showed a 16% removal of FLG with an initial concentration of 1 mg·L⁻¹. The removal data for GO and FLG were fitted using the Freundlich equation (R² = 0.55, 0.94, respectively). The data presented in this study for carbonaceous NM removal from wastewater provides quantitative information for environmental exposure modeling and life cycle assessment.     

Higher trophic level prey does not represent a higher quality diet in a threatened seabird: implications for relating population dynamics to diet shifts inferred from stable isotopes

Diet quality is a key determinant of population dynamics. If a higher trophic level, more fish-based diet is of higher quality for marine predators, then individuals with a higher trophic level diet should have a greater body mass than those feeding at a lower trophic level. We examined this hypothesis using stable isotope analysis to infer dietary trophic level and foraging habitat over three years in eastern rockhopper penguins Eudyptes chrysocome filholi on sub-Antarctic Campbell Island, New Zealand. Rockhopper penguins are ‘Vulnerable’ to extinction because of widespread and dramatic population declines, perhaps related to nutritional stress caused by a climate-induced shift to a lower trophic level, lower quality diet. We related the stable nitrogen (δ¹⁵N) and carbon (δ¹³C) isotope values of blood from 70 chicks, 55 adult females, and 55 adult males to their body masses in the 2010, 2011, and 2012 breeding seasons and examined year, stage, age, and sex differences. Opposite to predictions, heavier males consumed a lower trophic level diet during incubation in 2011, and average chick mass was heavier in 2011 when chicks were fed a more zooplankton-based, pelagic/offshore diet than in 2012. Contrary to the suggested importance of a fish-based diet, our results support the alternative hypothesis that rockhopper penguin populations are likely to be most successful when abundant zooplankton prey are available. We caution that historic shifts to lower trophic level prey should not be assumed to reflect nutritional stress and a cause of population declines.