Heidi Birch

Passive Dosing to Determine the Speciation of Hydrophobic Organic Chemicals in Aqueous Samples

A new analytical approach to determine the speciation of hydrophobic organic analytes is presented. The freely dissolved concentration in a sample is controlled by passive dosing from silicone (poly(dimethylsiloxane)), and the total sample concentration at equilibrium is measured. The free fraction is determined as the ratio between measured concentrations in pure water and sample. (14)C-labeled fluoranthene served as model analyte, and total sample concentrations were easily measured by liquid scintillation counting. The method was applied to surface water, stormwater runoff, and wastewater. In the untreated wastewater, 61% of the fluoranthene was bound to suspended solids, 28% was associated to dissolved organic matter, and 11% was freely dissolved, while in treated wastewater, the speciation was 16% bound to suspended solids, 4% bound to dissolved organic matter, and 80% freely dissolved. The free fraction in roof runoff (85%) and surface water (91%) was markedly higher than in runoff from paved areas, which ranged from 27 to 36%. A log K(DOC) value of 5.26 was determined for Aldrich humic acid, which agrees well with reported values obtained by fluorescence quenching and solid phase microextraction (SPME). This analytical approach combines simplicity with high precision, and it does not require any phase separation steps.

Velocity dependent passive sampling for monitoring of micropollutants in dynamic stormwater discharges.

Micropollutant monitoring in stormwater discharges is challenging because of the diversity of sources and thus large number of pollutants found in stormwater. This is further complicated by the dynamics in runoff flows and the large number of discharge points. Most passive samplers are nonideal for sampling such systems because they sample in a time-integrative manner. This paper reports test of a flow-through passive sampler, deployed in stormwater runoff at the outlet of a residential-industrial catchment. Momentum from the water velocity during runoff events created flow through the sampler resulting in velocity dependent sampling. This approach enables the integrative sampling of stormwater runoff during periods of weeks to months while weighting actual runoff events higher than no flow periods. Results were comparable to results from volume-proportional samples and results obtained from using a dynamic stormwater quality model (DSQM). The paper illustrates how velocity-dependent flow-through passive sampling may revolutionize the way stormwater discharges are monitored. It also opens the possibility to monitor a larger range of discharge sites over longer time periods instead of focusing on single sites and single events, and it shows how this may be combined with DSQMs to interpret results and estimate loads over extended time periods.

Determining Biodegradation Kinetics of Hydrocarbons at Low Concentrations: Covering 5 and 9 Orders of Magnitude of Kow and Kaw

A partitioning-based experimental platform was developed and applied to determine primary biodegradation kinetics of 53 hydrocarbons at ng/L to μg/L concentrations covering C8-C20, 11 structural classes, and several orders of magnitude in hydrophobicity and volatility: (1) Passive dosing from a loaded silicone donor was used to set the concentration of each hydrocarbon in mixture stock solutions; (2) these solutions were combined with environmental water samples in gastight auto sampler vials for 1-100 days incubation, and (3) automated solid phase microextraction (SPME) coupled to GC-MS was applied directly on these test systems for measuring primary biodegradation relative to abiotic controls. First order biodegradation kinetics were obtained for 40 hydrocarbons in activated sludge filtrate, 18 in seawater, and 21 in lake water. Water phase half-lives in seawater and lake water were poorly related to hydrophobicity and volatility but were, with a few exceptions, within a factor of 10 or shorter than BioHCwin predictions. The most persistent hydrocarbons, 1,1,4,4,6-pentamethyldecalin, perhydropyrene, 1,2,3,6,7,8-hexahydropyrene, and 2,2,4,4,6,8,8-heptamethylnonane, showed limited or inconsistent degradation in all three environmental media. This biodegradation approach can cover a large chemical space at low substrate concentrations, which makes it highly suited for optimizing predictive models for environmental biodegradation.

Model-based monitoring of stormwater runoff quality

Monitoring of micropollutants (MP) in stormwater is essential to evaluate the impacts of stormwater on the receiving aquatic environment. The aim of this study was to investigate how different strategies for monitoring of stormwater quality (combining a model with field sampling) affect the information obtained about MP discharged from the monitored system. A dynamic stormwater quality model was calibrated using MP data collected by automatic volume-proportional sampling and passive sampling in a storm drainage system on the outskirts of Copenhagen (Denmark) and a 10-year rain series was used to find annual average (AA) and maximum event mean concentrations. Use of this model reduced the uncertainty of predicted AA concentrations compared to a simple stochastic method based solely on data. The predicted AA concentration, obtained by using passive sampler measurements (1 month installation) for calibration of the model, resulted in the same predicted level but with narrower model prediction bounds than by using volume-proportional samples for calibration. This shows that passive sampling allows for a better exploitation of the resources allocated for stormwater quality monitoring.

Biodegradation of hydrocarbon mixtures in surface waters at environmentally relevant levels – Effect of inoculum origin on kinetics and sequence of degradation

Biodegradation is a dominant removal process for many organic pollutants, and biodegradation tests serve as tools for assessing their environmental fate within regulatory risk assessment. In simulation tests, the inoculum is not standardized, varying in microbial quantity and quality, thereby potentially impacting the observed biodegradation kinetics. In this study we investigated the effect of inoculum origin on the biodegradation kinetics of hydrocarbons for five inocula from surface waters varying in urbanization and thus expected pre-exposure to petroleum hydrocarbons. A new biodegradation method for testing mixtures of hydrophobic chemicals at trace concentrations was demonstrated: Aqueous solutions containing 9 hydrocarbons were generated by passive dosing and diluted with surface water resulting in test systems containing native microorganisms exposed to test substances at ng-μg/L levels. Automated Headspace Solid Phase Microextraction coupled to GC-MS was applied directly to these test systems to determine substrate depletion relative to abiotic controls. Lag phases were generally less than 8 days. First order rate constants were within one order of magnitude for each hydrocarbon in four of the five waters but lower in water from a rural lake. The sequence of degradation between the 9 hydrocarbons showed similar patterns in the five waters indicating the potential for using selected hydrocarbons for benchmarking between biodegradation tests. Degradation half-times were shorter than or within one order of magnitude of BioHCwin predictions for 8 of 9 hydrocarbons. These results showed that location choice is important for biodegradation kinetics and can provide a relevant input to aquatic exposure and fate models.