Mark L. Hanson

The fate and persistence of trifluoroacetic and chloroacetic acids in pond waters

The environmental fate of trichloro-, dichloro-, and monochloroacetic acids, and trifluoroacetic acid was investigated using field aquatic microcosms and laboratory sediment-water systems. Trifluoroacetic acid was extremely persistent and showed no degradation during a one-year field study, though it appeared to undergo transient partitioning within an unknown pond phase as the temperature of the surroundings was reduced. Of the three chloroacetic acids, trichloro had the longest residence time (induction and decay) (approximately 40 d), dichloro the shortest (approximately 4 d), and monochloro an intermediate residence time (approximately 14 d). Laboratory studies suggest that the biodegradation of trichloro-, dichloro-, and monochloroacetic acids leads primarily to the formation of chloride and oxalic, glyoxalic, and glycolic acids, respectively.

Evaluation of monochloroacetic acid (MCA) degradation and toxicity to Lemna gibba, Myriophyllum spicatum, and Myriophyllum sibiricum in aquatic microcosms

The fate of monochloroacetic acid (MCA), a common phytotoxic aquatic contaminant, and its toxicity to the aquatic macrophytes Lemna gibba (L. gibba), Myriophyllum spicatum (M. spicatum), and Myriophyllum sibiricum (M. sibiricum) under semi-natural field conditions was studied. Replicate 12,000 l enclosures were treated with 0, 3, 10, 30 and 100 mg/l of MCA. Each microcosm was stocked with eight individual apical shoots of M. spicatum and M. sibiricum 1 day prior to initiation of exposure. Plants were sampled after 4, 7, 14 and 28 days of exposure and their response assessed using numerous somatic and biochemical endpoints. L. gibba was introduced into the microcosms the day of MCA treatment and monitored regularly for 21 days. The half-life of MCA in the water column ranged between 86 and 523 h. The most sensitive plant species was M. spicatum, followed by M. sibiricum and L. gibba. All species demonstrated toxicity within a threefold range of each other. Endpoint sensitivity varied depending on the duration of exposure and the level of effect chosen. Most species endpoint EC(x) values were less than an order of magnitude different. Citrate levels in Myriophyllum spp. were not influenced by exposure to MCA. The toxicity of MCA to M. spicatum and M. sibiricum was very similar and thus highly predictive of toxicity observed for each other. The EC(10) was a more conservative estimate of toxicity than the statistically derived no observed effect concentration. Current concentrations of MCA are not likely to pose a risk to these aquatic plants in surface waters.

Trichloroacetic acid (TCA) and trifluoroacetic acid (TFA) mixture toxicity to the macrophytes Myriophyllum spicatum and Myriophyllum sibiricum in aquatic microcosms

Trichloroacetic acid (TCA) and trifluoroacetic acid (TFA) have been detected together in environmental water samples throughout the world. TCA may enter into aquatic systems via rainout as the degradation product of chlorinated solvents, herbicide use, as a by-product of water disinfection and from emissions of spent bleach liquor of kraft pulp mills. Sources of TFA include degradation of hydrofluorocarbons (HFCs) refrigerants and pesticides. These substances are phytotoxic and widely distributed in aquatic environments. A study to assess the risk of a binary mixture of TCA and TFA to macrophytes in aquatic microcosms was conducted as part of a larger study on haloacetic acids. M. spicatum and M. sibiricum were exposed to 0.1, 1, 3 and 10 mg/l of both TCA and TFA (neutralized with sodium hydroxide) in replicate (n = 3) 12000 l aquatic microcosms for 49 days in an one-way analysis of variance design. Each microcosm was stocked with 14 individual apical shoots per species. The plants were sampled at regular intervals and assessed for the somatic endpoints of plant length, root growth, number of nodes and wet and dry mass and the biochemical endpoints of chlorophyll-a, chlorophyll-b, carotenoid content and citric acid levels. Results indicate that there were statistically significant effects of the TCA/TFA mixture on certain pigment concentrations immediately after the start of exposure (2-7 days), but the plants showed no signs of stress thereafter. These data suggest that TCA/TFA mixtures at environmentally relevant concentrations do not pose a significant risk to these aquatic macrophytes.

Field level evaluation and risk assessment of the toxicity of dichloroacetic acid to the aquatic macrophytes Lemna gibba, Myriophyllum spicatum, and Myriophyllum sibiricum

Dichloroacetic acid (DCA), a haloacetic acid, is a common contaminant of aquatic ecosystems. A study to investigate potential phytotoxic effects on rooted and floating macrophytes (Myriophyllum spicatum, M. sibiricum, and Lemna gibba) was conducted. Replicate 12,000 L outdoor microcosms (n = 3) were treated with 3, 10, 30, and 100 mg/L of DCA that had been neutralized to the sodium salt, plus controls. Plants were sampled regularly over 21 days and assessed for a variety of endpoints including plant growth, root growth, number of nodes, wet and dry mass, chlorophyll-a, chlorophyll-b, carotenoids, and citrate levels. EC10, EC25, and EC50 values were calculated for each endpoint that exhibited a concentration-response. Overall, M. sibiricum was slightly more sensitive than M. spicatum to DCA exposure. The most sensitive plant endpoints were wet mass and plant length. Pigments showed no response with exposure to DCA. The probability of current concentrations of DCA in Canadian lake water and Swiss river waters exceeding thresholds of toxicity derived from single species effect measure distributions (EC10s) is << 0.01%. The use of effect measure distributions holds promise as a new risk assessment technique for aquatic plants. Currently, environmental levels of DCA do not pose a risk to these plants.

Trichloroacetic acid fate and toxicity to the macrophytes Myriophyllum spicatum and Myriophyllum sibiricum under field conditions

Trichloroacetic acid (TCA) has been detected in rain, snow, and river samples throughout the world. It may enter into natural water systems via herbicide use, as a by-product of water disinfection, from emissions of spent bleach liquor of kraft pulp mills, and as a natural fungal product. This compound is phytotoxic and likely to accumulate in aquatic environments. A study to assess the fate of TCA in semi-natural aquatic environments and the toxicity of TCA to rooted aquatic macrophytes was conducted. The experiment involved exposing three replicate 12000 l aquatic microcosms at the University of Guelph Microcosm Facility to 0.05, 0.5, 3, and 10 mg/l of TCA for 35 days in a one-way analysis of variance design. Each microcosm was stocked with 14 individual 5 cm apical shoots of Myriophyllum spicatum and M. sibiricum. The plants were sampled at regular intervals and assessed for the somatic endpoints of plant length, root growth, number of nodes and wet and dry mass and the biochemical endpoints of chlorophyll-a and chlorophyll-b, carotenoid content, and citric acid levels. TCA half-lives in the microcosms ranged from 190 to 296 h depending on the initial concentration of TCA. Myriophyllum spp. results indicate that while there were some statistically significant differences from controls, there were no biologically significant effects of TCA for any of the endpoints examined. These data suggest that TCA does not pose a significant risk to these macrophytes up to 10 mg/l, which typically exceeds environmentally relevant concentrations by several orders of magnitude.

Is ambient chitobiase activity a monitoring tool for impacts on secondary production in lotic systems

Chitobiase is one of two enzymes responsible for cleaving the chitin polymers that form arthropod exoskeletons and has been found to be predictive of secondary production for marine and freshwater zooplankton. Since chitobiase is re- leased into water during molting by aquatic arthropods, it is possible that ambient chitobiase activity may be a useful proxy of secondary production in aquatic systems. In the present study, surface water samples from the upper Tennessee River basin, USA, were collected and analyzed for chitobiase to determine how enzyme levels vary with season, water depth, and proximity to sewage treatment outfalls. Additionally, chitobiase activity was correlated with three pharmaceuti- cal compounds to assess if changes in chitobiase activity were associated with contaminants derived from sewage treat- ment plants. Chitobiase activity was significantly (p < 0.05) elevated in the fall relative to other seasons. Further, chitobiase activity displayed significant positive correlation (p < 0.05) between surface and subsurface samples and was negatively correlated (p < 0.05) with pharmaceutical concentrations in summer samples. These results indicate the potential for chitobiase as an assessment tool in estimating secondary production and as an ecotoxicological indictor.