Karsten Liber

Human Health Effects From Chronic Arsenic Poisoning–A Review

The ill effects of human exposure to arsenic (As) have recently been reevaluated by government agencies around the world. This has lead to a lowering of As guidelines in drinking water, with Canada decreasing the maximum allowable level from 50 to 25 μg/L and the U.S. from 50 to 10 μg/L. Canada is currently contemplating a further decrease to 5 μg/L. The reason for these regulatory changes is the realization that As can cause deleterious effects at lower concentrations than was previously thought. There is a strong relationship between chronic ingestion of As and deleterious human health effects and here we provide an overview of some of the major effects documented in the scientific literature. As regulatory levels of As have been decreased, an increasing number of water supplies will now require removal of As before the water can be used for human consumption. While As exposure can occur from food, air and water, all major chronic As poisonings have stemmed from water and this is usually the predominant exposure route. Exposure to As leads to an accumulation of As in tissues such as skin, hair and nails, resulting in various clinical symptoms such as hyperpigmentation and keratosis. There is also an increased risk of skin, internal organ, and lung cancers. Cardiovascular disease and neuropathy have also been linked to As consumption. Verbal IQ and long term memory can also be affected, and As can suppress hormone regulation and hormone mediated gene transcription. Increases in fetal loss and premature delivery, and decreased birth weights of infants, can occur even at low (<10 μg/L) exposure levels. Malnourished people have been shown to be more predisposed to As-related skin lesions. A large percentage of the population (30–40%) that is using As-contaminated drinking water can have elevated As levels in urine, hair and nails, while showing no noticeable clinical symptoms, such as skin lesions. It is therefore important to carry out clinical tests of As exposure. Factors combining to increase/decrease the ill effects of As include duration and magnitude of As exposure, source of As exposure, nutrition, age and general health status. Analytical determinations of As poisoning can be made by examining As levels in urine, hair and toenails. Communities and individuals relying on groundwater sources for drinking water need to measure As levels to ensure that their supplies are safe. Communities with water As levels greater than 5 μg/L should consider a program to document As levels in the population.

Isolation and characterization of naphthenic acids from Athabasca oil sands tailings pond water

A laboratory bench procedure was developed to efficiently extract naphthenic acids from bulk volumes of Athabasca oil sands tailings pond water (TPW) for use in mammalian oral toxicity testing. This solvent-based procedure involved low solvent losses and a good extraction yield with low levels of impurities. Importantly, labour-intensive centrifugation of source water to remove solids was avoided, allowing processing of much larger volumes of water compared with previous protocols. Naphthenic acids, present at an estimated concentration of 81 mg/l, were procured from 515.5 l of TPW at an overall extraction efficiency of approximately 85%. By using distillation to recover and recycle solvent, a high solvent:water ratio was maintained while actual solvent consumption was limited to 70 ml per liter of water processed. Electrospray ionization mass spectrometry suggested a highly heterogeneous naphthenic acid mixture that exhibited nearly identical proportions of monocyclic, polycyclic, and acyclic acids with molecular weights primarily between 220 and 360. Biphenyls, naphthalenes, and phenanthrene/anthracene were the most prominent impurities detected, but their levels were low (< or = 13 microg/l) even in a concentrated solution of the naphthenic acids (8549 mg/l). Naphthenic acids stored at 4 degrees C at this concentration were stable, exhibiting no significant change in concentration over a 10-month period. This bulk isolation procedure should be useful to others needing to process large volumes of tailings or other source water for the purpose of procuring moderate amounts of naphthenic acids.

The Impact of Metallic Coagulants on the Removal of Organic Compounds from Oil Sands Process-Affected Water

Coagulation/flocculation (CF) by use of alum and cationic polymer polyDADMAC, was performed as a pretreatment for remediation of oil sands process-affected water (OSPW). Various factors were investigated and the process was optimized to improve efficiency of removal of organic carbon and turbidity. Destabilization of the particles occurred through charge neutralization by adsorption of hydroxide precipitates. Scanning electron microscope images revealed that the resultant flocs were compact. The CF process significantly reduced concentrations of naphthenic acids (NAs) and oxidized NAs by 37 and 86%, respectively, demonstrating the applicability of CF pretreatment to remove a persistent and toxic organic fraction from OSPW. Concentrations of vanadium and barium were decreased by 67-78% and 42-63%, respectively. Analysis of surface functional groups on flocs also confirmed the removal of the NAs compounds. Flocculation with cationic polymer compared to alum, caused toxicity toward the benthic invertebrate, Chironoums dilutus, thus application of the polymer should be limited.

Effectiveness of Ozonation Treatment in Eliminating Toxicity of Oil Sands Process-Affected Water to Chironomus dilutus

Water soluble organic compounds (OCs), including naphthenic acids (NAs), are potentially toxic constituents of oil sands process-affected water (OSPW) that is generated during extraction of bitumen from Alberta oil sands. Ozonation can decrease concentrations of OCs in OSPW. However, effects of ozonated-OSPW on multicellular organisms are unknown. A 10-day and a chronic exposure of Chironomus dilutus to OSPW were conducted to assess effects on survival, growth, development, and behavior. Two separate batches of OSPW were treated with 30 or 80 mg ozone (O(3))/L. Wet body masses of larvae exposed to OSPW were 64 to 77% less than their respective controls (p < 0.001). However, both levels of ozonation significantly attenuated effects of OSPW on growth. Similarly, chronic exposure to untreated OSPW resulted in significantly less pupation than in the controls, with 31% and 71% less pupation of larvae exposed to the two batches of OSPW (p < 0.05). Emergence was significantly less for larvae exposed to OSPW, with 13% and 8% of larvae emerging, compared to 81% in controls (p < 0.0001). Both levels of ozonation of OSPW attenuated effects on emergence. These results suggest that OCs degraded by ozonation causes toxicity of OSPW toward C. dilutus, and that ozonation attenuates toxicity of OSPW.

Effects of insecticide exposure on feeding inhibition in mayflies and oligochaetes

The present study examined the effects of pulse exposures of the insecticide imidacloprid on the mayfly, Epeorus longinmanus Eaton (Family Heptageniidae), and on an aquatic oligochaete, Lumbriculus variegatus Miller (Family Lumbriculidae). Pulse exposures of imidacloprid are particularly relevant for examination, because this insecticide is relatively soluble (510 mg/L) and is most likely to be at effect concentrations during runoff events. Experiments examined the recovery of organisms after a 24-h pulse exposure to imidacloprid over an environmentally realistic range of concentrations (0, 0.1, 0.5, 1, 5, and 10 microg/L). Effects on feeding were measured by quantifying the algal biomass consumed by mayflies or foodstuffs egested by oligochaetes. Imidacloprid was highly toxic, with low 24-h median lethal concentrations (LC50s) in early mayfly instars (24-h LC50, 2.1 +/- 0.8 microg/L) and larger, later mayfly instars (24-h LC50, 2.1 +/- 0.5 microg/L; 96-h LC50, 0.65 +/- 0.15 microg/L). Short (24-h) pulses of imidacloprid in excess of 1 microg/L caused feeding inhibition, whereas recovery (4 d) varied, depending on the number of days after contaminant exposure. In contrast to mayflies, oligochaetes were relatively insensitive to imidacloprid during the short (24-h) pulse; however, immobility of oligochaetes was observed during a 4-d, continuous-exposure experiment, with 96-h median effective concentrations of 6.2 +/- 1.4 microg/L. Overall, imidacloprid reduced the survivorship, feeding, and egestion of mayflies and oligochaetes at concentrations greater than 0.5 but less than 10 microg/L. Inhibited feeding and egestion indicate physiological and behavioral responses to this insecticide.

Effects of exposure to oil sands process-affected water from experimental reclamation ponds on Chironomus dilutus

Effective detoxification of oil sands process-affected water (OSPW) is one issue associated with bitumen extraction in the Alberta oil sands. It has been suggested that reclamation ponds can be used to passively treat OSPW, potentially allowing for its safe return to the environment. In this study, OSPW was sampled in two batches (A and B) from the Syncrude Canada Ltd. West In-Pit (WIP) settling pond and from three experimental reclamation ponds - Big Pit, FE5, and TPW. Acute (10 d) and chronic (until adult emergence) exposures of Chironomus dilutus larvae to OSPW were conducted and survival, growth, development, and behavior were assessed. Masses of larvae exposed to WIP-OSPW were 64-77% less than the freshwater control (p < 0.001). Similarly, chronic exposure to WIP-OSPW resulted in significantly (p < 0.05) less pupation than in the freshwater control, with 31% (A) and 71% (B) less pupation of larvae exposed to WIP-OSPW. Rates of emergence were significantly less for larvae exposed to WIP-OSPW, with only 13% (A) and 8% (B) of larvae emerging as adults when exposed to WIP-OSPW, compared to 81% in the freshwater control (p < 0.0001). Pupation and emergence rates were significantly less in TPW than freshwater control (p < 0.05), but there were no differences observed in Big Pit or FE5. Lesser toxicity was observed in reclaimed OSPW compared to fresh OSPW and this coincided with lesser concentrations of NAs. The results presented are consistent with the hypothesis that an organic fraction is the cause of the toxicity of OSPW toward C. dilutus and that OSPW aged in reclamation ponds retains toxicity and therefore, more aggressive, targeted treatment of OSPW is required to accelerate decreases.

Effects of Chironomus tentans larval growth retardation on adult emergence and ovipositing success: implications for interpreting freshwater sediment bioassays

A laboratory study was conducted with Chironomus tentans to assess the significance of growth retardation of third-to fourth-instar larvae over a 10-d test period on long-term survival, adult emergence, and ovipositing success. Data were intended to provide interpretive guidance for the commonly used growth endpoint in 10-d sediment bioassays with C. tentans. Larval growth was controlled by using six feeding levels ranging from 0.2 to 5.9 mg dry weight Tetrafin® fish food per day. Mean 10-d survival was ≥88% at all feeding levels, but larval growth decreased significantly (p<0.05) with each decrease in feeding level. Cumulative successful emergence of adult C. tentans decreased significantly with decreasing larval growth. Mean times to emergence always increased with decreasing growth rates and effects were generally more pronounced for females than males. At the lowest 10-d mean growth where successful emergence occurred (0.27 mg), the times to emergence doubled relative to the times observed at the highest 10-d mean growth (1.03 mg). Ten-day larval growth retardation was strongly correlated with reduction in adult emergence success (r2 = 0.96). Growth retardations ≥64% resulted in 86–100% reductions in adult emergence. Growth retardation in the range of 35 to 50% equated with comparable percent reductions in adult emergence success. Although fewer females successfully emerged at 10-d growths of 0.37 and 0.74 mg relative to the highest 10-d growth (1.03 mg), ovipositing success of these females did not appear to be adversely affected by either their slower growth rates or their lower mean dry weights (0.62 and 0.99 mg, respectively). Growth of second generation larvae did not appear to be affected by maternal growth rate, but rather appeared to be solely correlated with their own feeding level.

Direct and indirect responses of a freshwater food web to a potent synthetic oestrogen

Endocrine-disrupting chemicals (EDCs) in municipal effluents directly affect the sexual development and reproductive success of fishes, but indirect effects on invertebrate prey or fish predators through reduced predation or prey availability, respectively, are unknown. At the Experimental Lakes Area in northwestern Ontario, Canada, a long-term, whole-lake experiment was conducted using a before-after-control-impact design to determine both direct and indirect effects of the synthetic oestrogen used in the birth control pill, 17α-ethynyloestradiol (EE2). Algal, microbial, zooplankton and benthic invertebrate communities showed no declines in abundance during three summers of EE2 additions (5–6 ng l−1), indicating no direct toxic effects. Recruitment of fathead minnow (Pimephales promelas) failed, leading to a near-extirpation of this species both 2 years during (young-of-year, YOY) and 2 years following (adults and YOY) EE2 additions. Body condition of male lake trout (Salvelinus namaycush) and male and female white sucker (Catostomus commersonii) declined before changes in prey abundance, suggesting direct effects of EE2 on this endpoint. Evidence of indirect effects of EE2 was also observed. Increases in zooplankton, Chaoborus, and emerging insects were observed after 2 or 3 years of EE2 additions, strongly suggesting indirect effects mediated through the reduced abundance of several small-bodied fishes. Biomass of top predator lake trout declined by 23–42% during and after EE2 additions, most probably an indirect effect from the loss of its prey species, the fathead minnow and slimy sculpin (Cottus cognatus). Our results demonstrate that small-scale studies focusing solely on direct effects are likely to underestimate the true environmental impacts of oestrogens in municipal wastewaters and provide further evidence of the value of whole-ecosystem experiments for understanding indirect effects of EDCs and other aquatic stressors.

In Situ–Based Effects Measures: Considerations for Improving Methods and Approaches

Abstract In situ-based effects measures have gained increased acceptance as a means to improve the link between cause and effect in aquatic ecotoxicological studies. These approaches have primarily been employed where more conventional laboratory tests with field collected samples and routine in-field community surveys have failed to provide reasonable answers with respect to causes of toxicity, primary routes of contaminant exposure, and what constitutes ecotoxicologically relevant contaminant levels, at least at a site-specific level. One of the main advantages provided by in situ tests compared to more conventional field-based monitoring approaches is that they provide better control over stressor exposure to a defined population of test animals under natural or near-natural field conditions. In situ techniques can also be used to avoid artifacts related to sampling, transport and storage of contaminated water and sediment intended for laboratory-based toxicity assessment. In short, they can reduce the need for laboratory to field extrapolation and, when conducted properly, in situ tests can provide improved diagnostic ability and high ecological relevance. This paper provides suggestions and considerations for designing in situ studies, choosing test species and test endpoints, avoiding or minimizing test artifacts, best addressing some of the limitations of in situ test techniques, and generally improving the overall quality of the in situ approach chosen.

Toxicity of uranium, molybdenum, nickel, and arsenic to Hyalella azteca and Chironomus dilutus in water-only and spiked-sediment toxicity tests

A series of laboratory spiked-sediment toxicity tests with the amphipod Hyalella azteca and the midge Chironomus dilutus were undertaken to determine acute and chronic toxicity thresholds for uranium (U), molybdenum (Mo), nickel (Ni), and arsenic (As) based on both whole-sediment (total) and pore water exposure concentrations. Water-only toxicity data were also generated from separate experiments to determine the toxicities of these metals/metalloids under our test conditions and to help evaluate the hypothesis that pore water metal concentrations are better correlated with sediment toxicity to benthic organisms than whole-sediment metal concentrations. The relative toxicity of the four elements tested differed depending on which test species was used and whether whole-sediment or pore water metal concentrations were correlated with effects. Based on measured whole-sediment concentrations, Ni and As were the two most acutely toxic elements to H. azteca with 10-d LC50s of 521 and 532 mg/kg d.w., respectively. Measured pore water concentrations indicated that U and Ni were the two most acutely toxic elements, with 10-d LC50s to H. azteca of 2.15 and 2.05 mg/L, respectively. Based on pore water metal concentrations, the no-observed-effect concentrations (NOECs) for growth were (H. azteca and C. dilutus, respectively) 0.67 and 0.21 mg/L for U, <0.37 and 0.60 mg/L for Ni, and 16.43 and <0.42 mg/L for As. Pore-water lowest-observed-effect concentrations (LOECs) for growth were (H. azteca and C. dilutus, respectively) 2.99 and 0.48 mg/L for U, 0.37 and 2.33 mg/L for Ni, and 58.99 and 0.42 mg/L for As. For U and Ni, results from 96-h water-only acute toxicity tests correlated well with pore water metal concentrations in acutely toxic metal-spiked sediment. This was not true for As where metalloid concentrations in overlying water (diffusion from sediment) may have contributed to toxicity. The lowest whole-sediment LOEC reported here for As was 6.6- and 4-fold higher than the Canadian Council of Ministers of the Environment interim sediment quality guideline and the Canadian Nuclear Safety Commission (CNSC) lowest effect level (LEL), respectively. The lowest whole-sediment LOECs reported here for Ni, U and Mo were 4-, 17.5-, and >260-fold higher, respectively, than the CNSC LELs for these metals/metalloids. Data on pore water metal concentrations in toxic sediment would be a useful addition to future Guidelines documents.