Deterministic risk assessment of firefighting water additives to aquatic organisms.

Past firefighting water additives were found to contain perfluorinated compounds that could persist in the environment resulting in potential adverse effects to biota. Since this revelation, manufacturers have introduced alternative firefighting water additives that are fluorine free, but few studies have investigated the fate and effects in the environment of these new additives. Firefighting water additives could enter aquatic ecosystems through run-off, leaching or direct application. Therefore, there is a need to investigate the potential effect that firefighting water additives could have on aquatic biota. This study investigated the toxicity of six firefighting water additives: Eco-Gel™, Thermo-Gel™, FireAde™, Fire-Brake™, Novacool Foam™, and F-500™ to aquatic biota. The toxicities of firefighting water additives to Lemna minor (duckweed), Daphnia magna (water flea), Hexagenia spp. larvae (mayfly), Lampsilis fasciola (wavy-rayed lampmussel) and Oncorhynchus mykiss (rainbow trout) were investigated through acute and chronic static and semi-static tests to estimate LC50 values for survival and EC50 values for immobility and/or reproduction endpoints. A large variation in toxicities among the firefighting water additives and among the test species was observed. Based on a worst-case exposure scenario of direct application, several firefighting water additives were found to pose a hazard to aquatic organisms. An exposure rate representative of a direct overhead application by a water bomber during a forest fire was used in the hazard assessment. For example, the hazard quotients determined for the D. magna acute toxicity tests ranged from 0.20 for Eco-Gel to 317 for F-500 in the forest pool (15 cm) scenario. This study presents the first deterministic risk assessment of firefighting water additives in aquatic ecosystems.

Sensitivity of larval and juvenile freshwater mussels (unionidae) to ammonia, chloride, copper, potassium, and selected binary chemical mixtures.

In aquatic environments, organisms such as freshwater mussels are likely exposed to complex contaminant mixtures related to industrial, agricultural, and urban activities. With growing interest in understanding the risk that chemical mixtures pose to mussels, this investigation focused on the effects of various waterborne contaminants (ammonia, chloride, copper, and potassium) and selected binary mixtures of these chemicals following a fixed-ratio design to Villosa iris glochidia and juvenile Lampsilis fasciola. In individual exposures, 48-h EC50 values were determined for V. iris glochidia exposed to ammonia chloride (7.4 [95% confidence interval (CI) 6.6-8.2] mg N/L), ammonia sulfate (8.4 [7.6-9.1] mg N/L), copper sulfate (14.2 [12.9-15.4] µg Cu2+/L), potassium chloride (12.8 [11.9-13.7] mg K+/L), potassium sulfate (10.1 [8.9-11.2] mg K+/L), and sodium chloride (480.5 [435.5-525.5] mg Cl-/L). The 7-d LC50 values for juvenile L. fasciola were determined for potassium sulfate (45.0 [18.8-71.2] mg K+/L), and sodium chloride (1738.2 [1418.6-2057.8] mg Cl-/L). In Ontario these waterborne contaminants have been reported to co-occur, with concentrations exceeding the EC10 for both life stages at some locations. Data from binary mixture exposures for V. iris glochidia (chloride-ammonia, chloride-copper, and copper-ammonia) and juvenile L. fasciola (chloride-potassium) were analyzed using a regression-based, dose-response mixture analysis modeling framework. Results from the mixture analysis were used to determine if an additive model for mixture toxicity [concentration addition (CA) or independent action (IA)] best described the toxicity of each mixture and if deviation towards dose-ratio (DR) or dose-level (DL) synergism/antagonism (S/A) occurred. For all glochidia binary mixture exposures, CA was the best fit model with DL deviation reported for the chloride-copper mixture and DR deviation reported for the copper-ammonia mixture. Using the model deviation ratio (MDR), the observed toxicity in all three glochidia mixture exposures were adequately described by both CA (mean = 0.71) and IA (mean = 0.97) whereas the juvenile mixture exposure was only adequately described by CA (mean = 0.64; IA mean = 0.05).

Bioaccumulation of perfluorinated carboxylates and sulfonates and polychlorinated biphenyls in laboratory-cultured Hexagenia spp., Lumbriculus variegatus and Pimephales promelas from field-collected sediments.

Polychlorinated biphenyls (PCBs) and perfluorinated carboxylates and sulfonates (PFASs) are persistent pollutants in sediment that can potentially bioaccumulate in aquatic organisms. The current study investigates variation in the accumulation of PCBs and PFASs in laboratory-cultured Hexagenia spp., Lumbriculus variegatus and Pimephales promelas from contaminated field-collected sediment using 28-day tests. BSAF(lipid) (lipid-normalized biota-sediment accumulation factor) values for total concentration of PCBs were greater in Hexagenia spp. relative to L. variegatus and P. promelas. The distribution of congeners contributing to the total concentration of PCBs in tissue varied among the three species. Trichlorobiphenyl congeners composed the greatest proportion of the total concentration of PCBs in L. variegatus while tetra- and pentabiphenyl congeners dominated in Hexagenia spp. and P. promelas. Perfluorooctane sulfonate (PFOS) was present in all three species at concentrations greater than all other PFASs analyzed. Hexagenia spp. also produced the greatest BSAF(lipid) and BSAF(ww) (non-lipid-normalized biota-sediment accumulation factor) values for PFOS relative to the other two species. However, this was not the case for all PFASs. The trend of BSAF values and number of carbon atoms in the perfluoroalkyl chain of perfluorinated carboxylates varied among the three species but was similar for perfluorinated sulfonates. Differences in the dominant pathways of exposure (e.g., water, sediment ingestion) likely explain a large proportion of the variation in accumulation observed across the three species.

Effect of biosolids-derived triclosan and triclocarban on the colonization of plant roots by arbuscular mycorrhizal fungi.

Arbuscular mycorrhizal fungi (AMF) form a symbiotic relationship with the majority of crop plants. AMF provide plants with nutrients (e.g., P), modulate the effect of metal and pathogen exposure, and increase tolerance to moisture stress. The benefits of AMF to plant growth make them important to the development of sustainable agriculture. The land application of biosolids is becoming an increasingly common practice in sustainable agriculture, as a source of nutrients. However, biosolids have been found to contain numerous pharmaceutical and personal care products including antimicrobial chemicals such as triclosan and triclocarban. The potential risks that these two compounds may pose to plant-AMF interactions are poorly understood. The current study investigated whether biosolids-derived triclosan and triclocarban affect the colonization of the roots of lettuce and corn plants by AMF. Plants were grown in soil amended with biosolids that contained increasing concentrations of triclosan (0 to 307 µg/g dw) or triclocarban (0 to 304 µg/g dw). A relationship between the concentration of triclosan or triclocarban and colonization of plants roots by AMF was not observed. The presence of biosolids did not have a significant (p>0.05) effect on percent colonization of corn roots but had a significant, positive effect (p<0.05) on lettuce roots. Biosolids-derived triclosan and triclocarban did not inhibit the colonization of crop plant roots by AMF.

Human health risk assessment of pharmaceuticals and personal care products in plant tissue due to biosolids and manure amendments, and wastewater irrigation.

Amending soil with biosolids or livestock manure provides essential nutrients in agriculture. Irrigation with wastewater allows for agriculture in regions where water resources are limited. However, biosolids, manure and wastewater have all been shown to contain pharmaceuticals and personal care products (PPCPs). Studies have shown that PPCPs can accumulate in the tissues of plants but the risk that accumulated residues may pose to humans via consumption of edible portions is not well documented. This study reviewed the literature for studies that reported residues of PPCPs in the edible tissue of plants grown in biosolids- or manure-amended soils or irrigated with wastewater. These residues were used to determine the estimated daily intake of PPCPs for an adult and toddler. Estimated daily intake values were compared to acceptable daily intakes to determine whether PPCPs in plant tissue pose a hazard to human health. For all three amendment practices, the majority of reported residues resulted in hazard quotients <0.1. Amendment with biosolids or manure resulted in hazard quotients ≥0.1 for carbamazepine, diphenhydramine, salbutamol, triclosan, and sulfamethazine. Irrigation with wastewater resulted in hazard quotients of ≥0.1 for ambrettolid, carbamazepine, diclofenac, flunixin, lamotrigine, metoprolol, naproxen, sildenafil and tonalide. [corrected]. Many of the residues that resulted in hazard quotients ≥0.1 were due to exposing plants to concentrations of PPCPs that would not be considered relevant based on concentrations reported in biosolids and manure or unrealistic methods of exposure, which lead to artificially elevated plant residues. Our assessment indicates that the majority of individual PPCPs in the edible tissue of plants due to biosolids or manure amendment or wastewater irrigation represent a de minimis risk to human health. Assuming additivity, the mixture of PPCPs could potentially present a hazard. Further work needs to be done to assess the risk of the mixture of PPCPs that may be present in edible tissue of plants grown under these three amendment practices.

The decline of the European eel Anguilla anguilla: quantifying and managing escapement to support conservation.

A method was developed to quantify the number and biomass of European eels Anguilla anguilla escaping to the ocean for breeding. The non-intrusive method, involving a fixed-position, high-frequency multi-beam sonar, permitted constant surveillance of A. anguilla movements throughout their 5 month escapement season (July to December). During this period, >1000 individuals were monitored escaping to the Atlantic Ocean from their freshwater habitat in the River Huntspill study site (Somerset, U.K.). The total length of each fish was measured using the sonar software. These measurements were then converted to an estimate of mass using a length:mass regression relationship derived from historical fyke-net data from this site, comprising c. 500 A. anguilla length:mass measurements collected over a 10 year period. The net biomass of escapement from the study site was equivalent to c. 6 kg ha⁻¹ year⁻¹, lower than the present European target which would require at least 7 kg ha⁻¹ year⁻¹ from this habitat. These findings demonstrate the capabilities of this monitoring technique and its usefulness both as a tool to assess the compliance with conservation targets and as a tool to evaluate the success of conservation measures for elusive aquatic species such as A. anguilla.

The effect of organism density on bioaccumulation of contaminants from sediment in three aquatic test species: a case for standardizing to sediment organic carbon.

Laboratory methods for measuring bioaccumulation of organic contaminants from sediment into aquatic organisms continue to improve, but some aspects are still in need of standardization. From a review of published methods, we noted that the loading density of organisms was determined inconsistently and was primarily based on either sediment volume or total organic carbon (TOC). The rationale mainly expressed for standardizing to TOC was to minimize the depletion of sediment contaminants. However, even when density was standardized to TOC, the relative amount of TOC provided (i.e., ratio of TOC to organism dry weight [dw]) was highly variable. In this study, we examined the effect of organism density (standardized to sediment TOC or volume) on bioaccumulation in three freshwater organisms. The oligochaete Lumbriculus variegatus, mayfly nymph Hexagenia spp., and fathead minnow Pimephales promelas were exposed for 28 days to two field-contaminated sediments that varied in concentration of PCBs and TOC. Densities tested were 50:1 and 27:1 ratios of TOC to organism dw and 140 ml sediment/g wet weight (ww) biomass, yielding low to high organism densities. Bioaccumulation in Hexagenia spp. was significantly higher at the lowest organism density compared with the highest organism density when exposed to site 2 sediment (1.1% TOC) but only with tissue concentrations expressed on a ww basis. Otherwise, there was no significant effect of density on bioaccumulation in organisms exposed to sediments from site 1 (12% TOC) or site 2. Survival of Hexagenia spp. was adversely affected at the highest organism density when the relative amount of TOC was low. The results of this study support the recommendation of standardizing organism density relative to a particular amount of TOC for invertebrate species. A 27:1 ratio of TOC:organism dw was selected as a standard organism density for a new bioaccumulation method because survival, growth, and bioaccumulation were not impacted relative to a 50:1 ratio, and less sediment was required. This density is recommended as an appropriate ratio for sediment bioaccumulation assessments in general.

Deposition in boreal forests in relation to type, size, number and placement of collectors.

Open precipitation and throughfall was collected at a Norway spruce stand in Finland using funnel-type collectors and at a black spruce stand in Canada using trough-type collectors. The presence or absence of a rim on the funnel, funnel diameter (9, 14 and 20 cm) and length of sampling period (1, 2 and 4 weeks) on monthly values were evaluated at the Norway spruce stand, and the number of collectors required for defined levels of accuracy and precision of throughfall loads to be reached and the influence of the spatial arrangement of collectors on solute concentrations was studied at both stands. The presence of a rim had no significant effect on open precipitation and throughfall amounts, but did on throughfall DOC, Ca(2+), Mg(2+), K(+), Na(+) and Cl(-) ion loads. Deposition loads increased with decreasing funnel diameter; for open precipitation, this was due to increased catch efficiency while for throughfall the increase was attributed to canopy interaction and leaching of litter trapped in the collectors. Calculated monthly H(+) loads decreased and those for all other constituents increased with collection period length. Using 15 collectors at the Norway spruce stand would allow throughfall loads to be determined to within 20% of the true mean weekly value with a confidence level of 95% for most solute, but not for NH(4) (+)-N, NO(3) (-)-N, Mg(2+) and SO(4) (2-)-S. Using 15 trough collectors, the same confidence level at the more heterogeneous black spruce stand would only be achieved for H(+), Cl(-), DOC and SO(4) (2-)-S loads. In both stands, using either random or systematic placements of throughfall collectors gave similar results.

Microcosm evaluation of the toxicity and risk to aquatic macrophytes from perfluorooctane sulfonic acid.

Perfluorooctane sulfonic acid (PFOS) is an anthropogenic contaminant detected in various environmental and biologic matrices. This compound is a fluorinated surfactant, a class of molecules renowned for their persistence and their global distribution but for which few ecotoxicological data are currently available, especially under field conditions. The toxicity of PFOS to the aquatic macrophytes Myriophyllum sibiricum and M. spicatum was investigated using 12,000 L outdoor microcosms. Replicate microcosms (n = 3) were treated with 0.3, 3, 10, and 30 mg/L PFOS as the potassium salt and assessed at regular intervals during a period of 42 days. M. sibiricum was more sensitive to PFOS under these simulated field conditions than M. spicatum. Toxicity was observed in the evaluated end points at > 3 mg/L PFOS for EC10s and > 12 mg/L PFOS for EC50s for M. spicatum and in M. sibiricum at > 0.1 mg/L PFOS for EC10s and > 1.6 mg/L PFOS for EC50s. The no observed-effect concentration (NOEC) for M. spicatum was consistently > or = 11.4 mg/L PFOS, whereas the NOEC for M. sibiricum was > or = 0.3 mg/L PFOS. A risk assessment for these plants estimated a negligible probability of toxicity being observed in these plants from PFOS exposure at current environmental concentrations.

Response of zooplankton and phytoplankton communities to creosote-impregnated Douglas fir pilings in freshwater microcosms.

Creosote has been used extensively as an industrial wood preservative for the protection of marine pilings, railway ties, and utility poles and is a common source of polycyclic aromatic hydrocarbons (PAHs) into aquatic environments. At present, there is little information by which to judge the potential for creosote leached from impregnated pilings to cause toxicity to biota in aquatic environments. The objective of the current study was to assess the effects of creosote on zooplankton and phytoplankton populations in freshwater microcosms in relation to changes in the concentration and composition of PAHs leached from creosote-impregnated Douglas fir pilings during an 83-day exposure period. The study consisted of single microcosms containing one half, one, two, three, four, and six treated pilings. Two microcosms that received untreated pilings were used as controls. The total surface area of pilings in each microcosm was normalized by adding the appropriate number of untreated pilings. Samples were collected periodically between -14 and 83 days pre- and postexposure to determine aqueous concentrations of 15 priority PAHs and to assess the response of zooplankton and phytoplankton communities. Plankton community response to creosote was analyzed using principle responses curves. Peak aqueous concentrations of sigmaPAH occurred at day 7, ranging from 7.3 to 97.3 microg/L. Zooplankton abundance decreased in all microcosms after introduction of the impregnated pilings, with the magnitude of response varying as a function of aqueous creosote concentration. Using inverse regression, a no-observed-effect concentration for the zooplankton community of 11.1 microg/L was estimated. In contrast, algal abundance and diversity increased in all treatments between 7 and 21 days and attained levels up to twice that in control microcosms. This trend most likely reflected decreased grazing pressure because of the decrease in zooplankton populations, but it may also have reflected growth stimulation resulting from exposure to various constituents within the creosote mixture. Our results indicate that creosote leached from impregnated pilings deployed under typical conditions (e.g., wharves) may cause transient toxicity to benthic or limnetic communities shortly after deployment, but this likely poses few long-term risks to aquatic freshwater plankton communities.

Laboratory evaluation of the toxicity of Perfluorooctane Sulfonate (PFOS) on Selenastrum capricornutum, Chlorella vulgaris, Lemna gibba, Daphnia magna, and Daphnia pulicaria.

Perfluorooctane sulfonate (PFOS) is an anthropogenic compound found in trace amounts in many environmental compartments far from areas of production. This, along with the highly persistent nature of PFOS, presents a concern for possible effects in aquatic ecosystems. The objective of this study was to determine the toxicity of PFOS in representative freshwater organisms. Toxicity testing using standard laboratory protocols was performed on the green algae Selenastrum capricornutum and Chlorella vulgaris, the floating macrophyte Lemna gibba, and the invertebrates Daphnia magna and Daphnia pulicaria. No observable effect concentration (NOEC) values were generated from the most sensitive endpoints for all organisms. Autotroph inhibition of growth NOEC values were 5.3, 8.2, and 6.6 mg/L for S. capricornutum, C. vulgaris, and L. gibba, respectively. The 48-h immobility NOEC values for D. magna and D. pulicaria were 0.8 and 13.6 mg/L, respectively. In comparison to immobility, the 21-day lethality NOEC for D. magna was 5.3 mg/L. Based on effect (immobility) values, the most sensitive of all test organisms was D. magna. The most sensitive organism based on 50% inhibition of growth (IC(50)) was L. gibba, with an IC(50) value of 31.1 mg/L determined from wet weight. This is 4.3 times less than the LC(50) for D. pulicaria, which was 134 mg/L. Significant adverse effects (p < or = 0.05) were observed for all organisms in concentrations >134 mg/L. The results indicate that under laboratory conditions PFOS is acutely toxic to freshwater organisms at concentrations at or near 100 mg/L. Based on known environmental concentrations of PFOS, which occur in the low ng/L to low microg/L range, there is no apparent risk to freshwater systems. However, further work is required to investigate long-term effects in these and other freshwater organisms.

Assessment of the probabilistic ecological risk assessment-toxic equivalent combination approach for evaluating pesticide mixture toxicity to zooplankton in outdoor microcosms.

The probabilistic ecological risk assessment-toxic equivalent (PERA-TE) combination approach was recently introduced in response to the increased demand for risk assessment approaches that can accommodate mixtures. The effectiveness and validity of the PERA-TE approach was assessed using two types of pesticide mixtures tested in outdoor microcosms. The first type of mixture consisted of pesticides with similar modes of action (the organophosphorus insecticides chlorpyrifos and diazinon) and the second of pesticides with different modes of action (chlorpyrifos, endosulfan, and trifluralin). To assess the toxicity of, and potential interaction within, each type of mixture, theoretically equitoxic TE mixtures were prepared in different proportional ratios. The TE mixtures were based on the 10th centile of acute toxicity effects distributions (data obtained from the literature) and a factor of the sum of the 90th centile field concentrations extrapolated from exposure distributions based on North American surface water monitoring data. Changes in zooplankton population abundances were used as the effect measure. The binary organophosphorus mixtures were equitoxic and conformed to the concentration addition model. The observed response trends of zooplankton exposed to the mixture of chemicals with different modes of action were a result of the susceptibility of individual taxa to the dominating pesticide in each mixture. Overall, the PERA-TE approach was not effective in predicting the toxicity and interaction of all mixture types and should be limited to assessing mixtures of chemicals with similar modes of action.

Factors affecting reproduction and the importance of adult size on reproductive output of the midge Chironomus tentans.

We conducted two separate tests to evaluate the influence of several factors that could affect estimation and interpretation of effects on reproductive output of Chironomus tentans in sediment toxicity tests. Specifically, the influence of adult size, mating frequency in males (male), and age of both males and females (female) at first mating on mating success (number of successful matings), fecundity (number of eggs/female), percentage hatch, and number of offspring (number of hatched eggs) was assessed. In the first experiment, the influence of adult size on reproductive output was determined by growing midges fed a low (0.29 mg/individual/d) and a high (0.42 mg/individual/d) amount of food to produce small (S) and large (L) adults, respectively. The adults were then mated in one of four scenarios: S male x S female, S male x L female, L male x S female, and L male x L female. An increase in male weight at a constant female weight had no significant effect on fecundity, whereas an increase in female weight yielded 49.5 and 60.7% increases in fecundity when mated with low- and high-fed males, respectively. Similarly, mean number of offspring (fecundity x percent hatch) increased by 19.8 and 48.3% when male weight was increased and female weight was held constant and by 141.9 and 180.4% when female weight was increased and male weight was held constant. In the second experiment, conducted at a single feeding rate, fecundity increased significantly with an increase in female weight but not male weight. The number of offspring was not significantly influenced by adult weight. The age of males or females at first mating, the frequency with which males were mated (up to seven consecutive days), and the proportion of males successfully mating had no effect on fecundity or number of offspring; however, large increases in variability about mean estimates were observed in some endpoints for older males. These results suggest that adult female size is the most important factor affecting reproductive output in C. tentans, and that enhanced performance of the life-cycle test with respect to all reproductive endpoints might be achieved if males are not mated for more than five consecutive days.

Amendment of sediments with a carbonaceous resin reduces bioavailability of polycyclic aromatic hydrocarbons.

We evaluated the effectiveness of Ambersorb, a carbonaceous resin, in reducing bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated sediments collected from the field. In laboratory studies, sediment pore-water concentrations of eight unsubstituted PAHs were significantly decreased after resin addition. Reduced PAH concentrations in oligochaete tissues from a laboratory bioaccumulation test, along with increased survival/reproduction and reduced photo-enhanced toxicity and sediment avoidance, also resulted from sediment treatment with Ambersorb. Resin amendment also decreased pore-water PAH concentrations in field deployed sediments but did not improve benthic invertebrate colonization. Prediction of partitioning of PAHs between solid and aqueous phases in the test sediments was complicated by the presence of coal and soot. However, accurate predictions of bioavailability were achieved based on pore-water chemistry. Overall, these studies show that the addition of high affinity sorbents effectively reduces pore-water PAH concentrations and bioavailability and suggests that sorbent addition may serve as an option for in situ remediation of some contaminated sediments.

Response of zooplankton communities to liquid creosote in freshwater microcosms.

In this study, the response of zooplankton communities to single applications of liquid creosote in model aquatic ecosystems (microcosms) was evaluated. Liquid creosote was applied to 14 microcosms at concentrations ranging from 0.06 to 109 mg/L. Two microcosms served as controls. Zooplankton samples were collected from each microcosm on days 7 and 1 before treatment and on days 2, 5, 7, 14, 21, 28, 43, 55, and 83 following treatment. Temporal changes (response-recovery) in composition of the zooplankton community were assessed using principal response curves (PRC). Creosote induced a rapid, concentration-dependent reduction in zooplankton abundance and number of taxa, with maximum response (50-100% reduction in population densities) occurring between 5 and 7 d after treatment. Taxa that dominated at the time of treatment experienced the greatest impact, as indicated by large, positive species weight values (> 1) from the PRC analysis. Many of these taxa recovered to pretreatment or control levels during the posttreatment period, with the degree and duration of recovery being strongly dependent on concentration. Creosote had little effect on species composition at less than 1.1 mg/L, because changes in the types and relative proportion of species contributed from Cladocera, Rotifera, and Copepoda were comparable to those observed in control microcosms. However, a significant shift in species composition was observed at concentrations greater than 1.1 mg/L; these microcosms were generally dominated by low numbers of rotifers, some of which had not been collected before treatment. Community-level effect concentrations (EC50s) were 44.6 and 46.6 micrograms/L at 5 and 7 d, respectively, based on nominal creosote. Corresponding no-effect concentrations were 13.9 and 5.6 micrograms/L. The results of this field study indicate that creosote may pose a significant risk to zooplankton communities at environmental concentrations potentially encountered during spills and/or leaching events.

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.

Chlorodifluoroacetic acid fate and toxicity to the macrophytes Lemna gibba, Myriophyllum spicatum, and Myriophyllum sibiricum in aquatic microcosms.

Chlorodifluoroacetic acid (CDFA) is a novel haloacetic acid (HAA) and has been recently documented in aquatic systems. It is a suspected degradation product of the refrigerants 1,1,2-trichloro-1,1-difluoroethane (CFC-113) and 1-chloro-1,1-difluoroethane (HCFC-142b). Haloacetic acids can be phytotoxic, putatively acting through inhibition of the citric acid cycle. Replicate (n = 3) 12,000-L model aquatic ecosystems (microcosms) were dosed once at 0.5, 1, 5, and 20 mg/L of neutralized CDFA. Three microcosms served as controls. Each microcosm was stocked with eight individual apical shoots of both Myriophyllum spicatum and Myriophyllum sibiricum and sampled at regular intervals over a 42-d exposure period. The plants were assessed for the somatic endpoints of plant length, root growth, node number, and wet and dry mass and the biochemical endpoints of chlorophyll-a/b and carotenoid content as well as citric acid levels. The duckweed Lemna gibba was also introduced into these systems and monitored over a period of 14 d for wet/dry mass, plant/frond number, chlorophyll content, and growth rate. Concentrations of CDFA remained constant in the water column over the course of the fate investigation (241 d), indicating that this compound undergoes little, if any, degradation in aquatic systems. Results showed few statistically significant differences from controls for all three plant species with exposure to CDFA but no biologically relevant impacts. Overall, CDFA does not appear to pose any risk to these aquatic macrophytes at current environmental concentrations.

Response of phytoplankton communities to liquid creosote in freshwater microcosms.

We assessed the response of phytoplankton communities in aquatic microcosms to single applications of liquid creosote. The creosote was applied to 14 microcosms at concentrations ranging from 0.06 to 109 mg/L. Two microcosms served as controls. Phytoplankton samples were collected from each microcosm one week and 1 d before treatment and at 7 and 21 d after treatment. Temporal changes (response-recovery) in phytoplankton community composition were assessed with principal response curves. Creosote had no direct toxic effect on the phytoplankton community based on total abundance and number of taxa. Population levels declined in all treatments between day -1 and day 7, but this trend mirrored a similar decline in the control microcosms. At both 7 and 21 d after treatment, population densities and number of taxa in most treatments exceeded those in the controls and exhibited a parabolic relationship relative to creosote concentration. This relationship was most pronounced at 21 d, at which time population densities and number of taxa at intermediate concentrations were up to twice those at low and high concentrations. This response pattern seems to represent an indirect response to impacts on zooplankton and a corresponding reduction in grazing pressure. In contrast, total algal biomass declined 52 to 97% relative to the controls at all but the lowest creosote concentration at 7 d. This apparent decline was due to a significant proliferation of the alga Closterium moniliforme in the controls and low creosote concentration. At 21 d, no difference was found in total biomass between treated and control microcosms. The results of this study suggest that creosote does not pose a significant direct risk to phytoplankton at concentrations likely to be encountered in most contaminated aquatic environments; however, stimulation of algal populations could occur in situations of long-term chronic exposure or spill events that remove predatory zooplankton populations.