The effect of suspended particles coated by humic acid on the toxicity of pharmaceuticals, estrogens, and phenolic compounds

The sorption characteristics of 10 organic chemicals, categorized as pharmaceuticals, estrogens and phenols, onto synthetic suspended particle (i.e., alumina) coated with humic acid were investigated according to their octanol-water partition coefficient (K(ow)). Chemical analyses were performed with gas chromatography and mass spectrometry (GC/MS) and high performance liquid chromatography (HPLC). The effects of particles on the toxicity reduction were evaluated using bioassay tests, using Daphnia magna and Vibrio fisheri for phenols and pharmaceuticals, and the human breast cancer cell MCF-7 for estrogens. Sorption studies revealed that 22 and 38% of octylphenol and pentachlorophenol, respectively, were removed by suspended particle, whereas 2,4-dichlorophenol was not removed, which was directly proportional to the logK(ow) value. Similar to the sorption tests, suspended particles significantly reduced the acute toxicities of octylphenol and pentachlorophenol to D. magna and V. fisheri (p<0.01), but there was no significant difference in the toxicity of 2,4-dichlorophenol to D. magna (p=0.8374). Pharmaceuticals, such as ibuprofen, gemfibrozil and tolfenamic acid, showed no discernible sorption to the suspended particle, with the exception of diclofenac, which revealed 11% sorption. For estrogens, such as estrone, 17beta-estradiol and 17alpha-ethynylestradiol, the results indicated no reduction in the sorption test. This may be attributed to the polar interaction by functional groups in sorption between pharmaceuticals and estrogens and suspended particles. In the bioassays, presence of suspended particles did not significantly modify the toxicity of pharmaceuticals (regardless of their K(ow) values) to D. magna, V. fisheri or E-screen.     

Copepod recruitment and food composition: do diatoms affect hatching success?

Laboratory experiments were conducted to differentiate between factors controlling the hatching success of copepod eggs. Factors that could affect viability of eggs; viz food quality, female condition and external factors were investigated. In a series of experiments the copepod Acartia tonsa Dana was fed several different diets while egg production and hatching success were monitored. The diet was analysed for fatty acid content as an indicator of food quality. Both egg production and hatching were found to be affected by the nutritional quality of the food. Hatching was also highly dependent on female fertility. External effects were tested by exposing eggs to diatom extracts. Negative effects were only evident at high extract concentrations, but disappeared when aeration was supplied to the solution. Oxygen measurements showed that failure to hatch was due to hypoxia in the extracts. No inhibitory or toxic effects of diatom cell components on hatching could be found.     

Does male harassment of females contribute to reproductive synchrony in the grey seal by affecting maternal performance?

We investigated the possibility that male harassment of lactating females differed in relation to time of birth in the grey seal, Halichoerus grypus, on Sable Island, Nova Scotia. This was done by comparing the frequency of male disturbances, maternal performance and pup growth for females that either gave birth during the peak of the pupping season or after the peak. Of the females, 58% gave birth in a 7-day period near the beginning of the pupping period, when the operational sex ratio was 2–4 females per male. Late in the pupping period the operational sex ratio reversed to about 1 female for every 2 males. The relative frequency of disturbances by males was significantly greater for late-pupping mothers than for peak-pupping ones (1.9 vs. 1.4 encounters/h). Females that gave birth late also were disturbed by males 3 times more often than females that gave birth during the peak (3.4 vs. 1.1 % of observation time). Late-pupping mothers spent 22% less time suckling (4.0 vs. 5.1 % of observation time), had 30% slower growing pups (1.7 vs. 2.4 kg/d), and weaned pups that were 16% lighter (45.6 vs. 54.0 kg). The effect of birth time on pup mass gain and weaning mass was not attributable to factors such as maternal mass, pup birth mass or pup sex. We conclude that the reduced maternal performance is likely the result of the increased male harassment. As reduced weaning mass can lead to reduced juvenile survival, male harassment may have contributed to the enhanced reproductive synchrony in this species.     

Microbial relationships in surface-mine revegetation

The establishment and interrelationships of microorganisms with soil and plant processes during reclamation are greatly influenced by the composition of the planting medium and vegetation practices. While in some instances the parent material may be used as the vegetation medium, the practice of topsoiling, particularly the direct haul method, may be beneficial in introducing microorganisms and improving the quality of the plant growth medium of spoils that are chemically or physically less desirable than the native soils. The influence of different vegetation types on soil development on surface mines may be a reflection of physioiogical differences that affect microbial development in the rhizosphere. Such differences include levels of carbohydrate translocated to the root system and/or released into the surrounding soil; the plant's effectiveness as a mycorrhizal host; and the rate of degradation of plant residues. It has become apparent that microbial interactions are an important part of plant and soil processes in reclamation. While some of the microorganisms important in plant growth and soil development can be introduced readily by management practices, the majority usually are disseminated by natural means and only gradually become a part of the microbial population. More research is needed on developing new methods or refining current procedures for early introduction of these microorganisms in reclamation practices.     

Pretreatment of sludge with microwaves for pathogen destruction and improved anaerobic digestion performance.

A new way of generating Class A sludge using microwaves was evaluated through a series of laboratory-scale experiments. Microwaves provide rapid and uniform heating throughout the material. Other benefits of microwave treatment include instant and accurate control and selective and concentrated heating on materials, such as sludge, that have a high dielectric loss factor. Sludge was irradiated with 2450-MHz microwaves, and fecal coliforms were counted. Fecal coliforms were not detected at 65 degrees C for primary sludge and anaerobic digester sludge and at 85 degrees C for waste activated sludge when sludge was irradiated with 2450-MHz microwaves. During the bench-scale anaerobic digester operation, the highest average log reduction of fecal coliforms was achieved by the anaerobic digester fed with microwave-pretreated sludge (> or = 2.66 log removal). The anaerobic digester fed with microwave-irradiated sludge was more efficient in inactivation of fecal coliforms than the other two digesters fed with raw sludge and externally heated sludge, respectively. It took more than three hydraulic retention times for a bench-scale mesophilic anaerobic digester to meet Class A sludge requirements after feeding microwave-irradiated sludge. Class A sludge can be produced consistently with a continuously fed mesophilic anaerobic digester if sludge is pretreated with microwaves to reach 65 degrees C.     

Modeling transport and deposition of contaminants to ecosystems of concern: a case study for the Laurentian Great Lakes

Transfer efficiency (TE) is introduced as a model output that can be used to characterize the relative ability of chemicals to be transported in the environment and deposited to specific target ecosystems. We illustrate this concept by applying the Berkeley-Trent North American contaminant fate model (BETR North America) to identify organic chemicals with properties that result in efficient atmospheric transport and deposition to the Laurentian Great Lakes. By systematically applying the model to hypothetical organic chemicals that span a wide range of environmental partitioning properties, we identify combinations of properties that favor efficient transport and deposition to the Lakes. Five classes of chemicals are identified based on dominant transport and deposition pathways, and specific examples of chemicals in each class are identified and discussed. The role of vegetation in scavenging chemicals from the atmosphere is assessed, and found to have a negligible influence on transfer efficiency to the Great Lakes. Results indicate chemicals with octanol-water (K(ow)) and air-water (K(aw)) partition coefficients in the range of 10(5)-10(7) and 10(-4)-10(-1) combine efficient transport and deposition to the Great Lakes with potential for biaccumulation in the aquatic food web once they are deposited. A method of estimating the time scale for atmospheric transport and deposition process is suggested, and the effects of degrading reactions in the atmosphere and meteorological conditions on transport efficiency of different classes of chemicals are discussed. In total, this approach provides a method of identifying chemicals that are subject to long-range transport and deposition to specific target ecosystems as a result of their partitioning and persistence characteristics. Supported by an appropriate contaminant fate model, the approach can be applied to any target ecosystem of concern.     

Analysis of heavy metals in foliage near a modern refuse incinerator

Heavy metals such as cadmium and lead are typically found at high levels in fly ash from refuse incinerators. In two earlier studies it was found that such heavy metals on grass or tree foliage in the vicinity of old refuse incinerators with relatively low stacks and limited or no emission control devices showed a high degree of correlation between diminishing foliar concentration and the logarithm of sampling distance from the incinerator. In the study reported here of the concentration of cadmium and lead on foliage near a modern refuse incinerator with a high stack and efficient emission controls, the foliar concentrations of the metals showed no significant diminution with sampling distance from the incinerator. Factors affecting heavy metal emissions from refuse incinerators and contamination of nearby areas are discussed.     

Persistence and runoff losses of 3 herbicides and chlorpyrifos from a corn field in the Lake Balaton watershed of Hungary

Corn is intensively cultivated in western Hungary in the basin of Lake Balaton, one of the most important water resources in eastern Europe. Pesticide runoff was measured in 1996 and 1997 from a typical corn field near Zalaegerszeg, Hungary, which drains into the Zala River, an important water source of Lake Balaton. Three herbicides, namely atrazine, acetochlor, and propizochlor, and the insecticide chlorpyrifos were applied to bare soil in a field with 5% slope and soil and runoff water pesticide concentrations were monitored. In 1997, a rainfall-runoff simulation experiment was conducted on a small sub-plot in order to measure pesticide runoff under reasonable worst-case conditions. Under natural rainfall almost all losses occurred in a large runoff event in 1996 one month after application in which 3% of atrazine and 1% of acetochlor was transported off the field. Propizochlor and chlorpyrifos losses in the same event were much lower: 0.2% and <0.01%, respectively, because of these chemicals' shorter persistence times in near-surface soil. The rainfall simulation produced only trace amounts of losses even though 4.1 cm was applied in 2 hours; the soil was extremely dry and only 0.2 cm runoff occurred containing less than 0.01% of all chemicals applied. The results suggest that intensive use of corn herbicides, which have been found to result in widespread contamination of water resources elsewhere, may be expected to have the same impact in the Balaton watershed depending on the amounts and intensities used in the basin.     

A direct passive method for measuring water and contaminant fluxes in porous media

This paper introduces a new direct method for measuring water and contaminant fluxes in porous media. The method uses a passive flux meter (PFM), which is essentially a self-contained permeable unit properly sized to fit tightly in a screened well or boring. The meter is designed to accommodate a mixed medium of hydrophobic and/or hydrophilic permeable sorbents, which retain dissolved organic/inorganic contaminants present in the groundwater flowing passively through the meter. The contaminant mass intercepted and retained on the sorbent is used to quantify cumulative contaminant mass flux. The sorptive matrix is also impregnated with known amounts of one or more water soluble 'resident tracers'. These tracers are displaced from the sorbent at rates proportional to the groundwater flux; hence, in the current meter design, the resident tracers are used to quantify cumulative groundwater flux. Theory is presented and quantitative tools are developed to interpret the water flux from tracers possessing linear and nonlinear elution profiles. The same theory is extended to derive functional relationships useful for quantifying cumulative contaminant mass flux. To validate theory and demonstrate the passive flux meter, results of multiple box-aquifer experiments are presented and discussed. From these experiments, it is seen that accurate water flux measurements are obtained when the tracer used in calculations resides in the meter at levels representing 20 to 70 percent of the initial condition. 2,4-Dimethyl-3-pentanol (DMP) is used as a surrogate groundwater contaminant in the box aquifer experiments. Cumulative DMP fluxes are measured within 5% of known fluxes. The accuracy of these estimates generally increases with the total volume of water intercepted.     

Toxicity of a complex mixture of atmospherically transported pesticides to Ceriodaphnia dubia

The presence of several anthropogenic chemicals has been documented in the atmosphere of the Canadian prairies. The deposition of these chemicals as a mixture is of importancesince little is known of the combined effects of these chemicalson aquatic organisms. This study was designed to evaluate theacute and chronic toxicity of a complex mixture of nineatmospherically transported pesticides to Ceriodaphniadubia. The nine selected pesticides (bromoxynil, dicamba, 2,4-D,MCPA, triallate, trifluralin, pentachlorophenol, lindane, and4,4-DDT) were detected in appreciable quantities in dryatmospheric deposits. The concentration of each pesticide in themixture was based on maximum measured daily dry deposition ratesfor central Canada, except for pentachlorophenol, which wasestimated based on atmospheric concentrations. The 48-h LC50estimate for C. dubia exposed to the pesticide mixture was174.60 g L^-1 (340 times the measured total dry deposition concentration). The estimated NOEC and LOEC for bothsurvival and reproduction, as determined in the 7-d chronic toxicity test, were 51.3 (100 times) and 154 g L^-1 (300 times), respectively. A basic risk assessment, using the toxic unit approach, suggested that the toxicity of the pesticide mixture was mainly due to 4,4-DDT. Overall, this atmospherically transported complex mixture of pesticides appearsto pose a negligible toxicological risk to non-target aquatic invertebrates such as zooplankton.