Identification of the Sediment-Associated Contaminants in the Illinois River Complex using Toxicity Identification Evaluation (TIE)

The final report for this project “Identification of the Sediment-Associated Contaminants in the Illinois River Complex using a Toxicity Identification Evaluation (TIE)”, conducted by Dr. Michael Lydy and W. Tyler Mehler, is comprised of the thesis of W. Tyler Mehler submitted to the Department of Zoology, Southern Illinois University – Carbondale in December 2009. In addition, two papers have been published which are based on this project: Mehler, W. Tyler, Jonathan D. Maul, Jing You, and Michael J. Lydy. 2009. "Identifying the causes of sediment-associated contamination in the Illinois River (USA) using whole-sediment toxicity identification evaluation." Environmental Toxicology and Chemistry 29(1): 158-167; Mehler, W. Tyler, Jing You, Jonathan D. Maul, and Michael J. Lydy. 2010. "Comparative analysis of whole sediment and porewater toxicity identification evaluation techniques for ammonia and non-polar organic contaminants." Chemosphere 78: 814-821. The thesis and research papers have been subjected to external scientific peer review and may not necessarily reflect the views of the Illinois Sustainable Technology Center.The difficulty of assessing risk of sediment-associated contaminant mixtures to benthic ecosystems is often attributed to understanding the bioavailable fraction of each contaminant. These issues have led to the development of the toxicity identification evaluation (TIE). Past pore water TIE testing on Illinois River sediments has indicated that ammonia was the primary contaminant. The current study, however, suggests that ammonia is no longer the primary contaminant of concern, but rather non-polar organics, including polycyclic aromatic hydrocarbons, are the primary cause for toxicity in the Illinois River Complex (IRC). Summer of 2007 testing showed that six out of the seven sites that proceeded to Phase I testing exhibited a significant increase in survival with the addition of the non-polar organic amendment powdered coconut charcoal (PCC), while zeolite (ammonia amendment) and Resin Tech SIR 300 (cationic metals amendment) did not significantly increase survival suggesting that non-polar organics are the source of toxicity. In addition, Phase II testing suggested that concentrations of PAHs were high enough to cause the observed toxicity, which confirmed the results of Phase I testing. Additional seasonal-based sampling (i.e., fall, winter, spring, and summer 2008) supported the summer findings, with little variation between toxicity and concentrations, with 46% of the sites being improved with the addition of PCC in Phase I testing. The results of Phase I and Phase II contradicted past pore water TIE studies as non-polar organics were suggested as the source of toxicity rather than ammonia. Thus, both pore water and whole sediment TIE methodologies were used on two selected sites. The results of this study suggested that discordance between the past pore water TIEs and the current whole sediment TIE were attributed to the methodologies and on a lesser note the test organisms used. The present study provides data that could be used in combination with previous work to more accurately characterize the sources and spatial trends of toxicity in Illinois River sediments for future risk assessment and mitigation. Furthermore, the present study showed that while TIE methodologies are a valuable tool in assessing risk associated with contaminants in aquatic system, further research in understanding the role that each TIE method may serve in risk assessment is also important.Illinois Sustainable Technology Center/Grant No. HWR07211published or submitted for publicationis peer reviewe

Identifying Organic Toxicants in Sediment Using Effect-Directed Analysis: A Combination of Bioaccessibility-Based Extraction and High-Throughput Midge Toxicity Testing

Toxicity identification evaluation (TIE) and effect-directed analysis (EDA) were integrated to diagnose toxicity drivers in a complex system, such as sediment. In TIE manipulation, XAD resin was utilized as an amending agent for characterizing organic toxicants, which also facilitate a large-volume bioaccessibility-based extraction for EDA purposes. Both raw sediments in TIE and extract fractions in EDA were tested with Chironomus dilutus for toxicity using whole-sediment testing and a high-throughput microplate assay. This allowed for a direct link between whole-sediment TIE and EDA, which strongly strengthened the characterization and identification of toxicants. Sediments amended with XAD resin, as part of the TIE, significantly reduced midge mortality compared with unamended sediments, suggesting that organics were one class of main toxicants. On the basis of bioaccessible concentrations in sediment measured by XAD extraction, a group of previously unidentified contaminants, synthetic polycyclic musks (versalide, tonalide, and galaxolide), were found to explain 32-73% of the observed toxicity in test sediments. Meanwhile, three pyrethroids contributed to an additional 17-35% of toxicity. Surprisingly, the toxicity contribution of musks and pyrethroids reached 58-442 and 56-1625%, respectively, based on total sediment concentrations measured by exhaustive extraction. This suggested that total sediment concentrations significantly overestimated toxicity and that bioavailability should be considered in toxicity identification. Identifying nontarget toxicants sheds a light on application of the integrated TIE and EDA method in defining causality in a complex environment

Spatial and temporal variation in toxicity and inorganic composition of hydraulic fracturing flowback and produced water

Hydraulic fracturing for oil and gas extraction produces large volumes of wastewater, termed flowback and produced water (FPW), that are highly saline and contain a variety of organic and inorganic contaminants. In the present study, FPW samples from ten hydraulically fractured wells, across two geologic formations were collected at various timepoints. Samples were analyzed to determine spatial and temporal variation in their inorganic composition. Results indicate that FPW composition varied both between formations and within a single formation, with large compositional changes occurring over short distances. Temporally, all wells showed a time-dependent increase in inorganic elements, with total dissolved solids increasing by up to 200,000 mg/L over time, primarily due to elements associated with salinity (Cl, Na, Ca, Mg, K). Toxicological analysis of a subset of the FPW samples showed median lethal concentrations (LC50) of FPW to the aquatic invertebrate Daphnia magna were highly variable, with the LC50 values ranging from 1.16% to 13.7% FPW. Acute toxicity of FPW significantly correlated with salinity, indicating salinity is a primary driver of FPW toxicity, however organic components also contributed to toxicity. This study provides insight into spatiotemporal variability of FPW composition and illustrates the difficulty in predicting aquatic risk associated with FPW.Funding provided by: Natural Sciences and Engineering Research Council of CanadaCrossref Funder Registry ID: http://dx.doi.org/10.13039/501100000038Award Number: RGPIN-2020-0415

Effect-Directed Analysis of Toxicants in Sediment with Combined Passive Dosing and in Vivo Toxicity Testing

Identifying key toxicants in sediment is a great challenge, particularly if nontarget toxicants are involved. To identify the contaminants responsible for sediment toxicity to <i>Chironomus dilutus</i> in Guangzhou reach of the Pearl River in South China, passive dosing and in vivo toxicity testing were incorporated into effect-directed analysis (EDA) to account for bioavailability. Fractionation of sediment extracts was performed with gel permeation chromatography and reverse phase liquid chromatography sequentially. Polydimethylsiloxane served as passive dosing matrix for midge bioassays. The fractions showing abnormal enzymatic response were subject to a nontarget analysis, which screened out 15 candidate toxicants. The concentrations of the screened contaminants (log-based organic carbon normalized) in sediments of 10 sites were compared to sediment toxicity (10 and 20 day mortality and 10 day enzymatic response) to <i>C. dilutus</i> using correlation analyses. The results suggested that oxidative stress induced by cypermethrin, dimethomorph, pebulate and thenylchlor may have in part caused the observed toxicity to <i>C. dilutus</i>. The present study shows that EDA procedures coupled with passive dosing and in vivo toxicity testing can be effective in identifying sediment-bound toxicants, which may pose high risk to benthic organisms but are not routinely monitored and/or regulated. The findings of the present study highlight the importance of incorporating environmentally relevant approaches in assessing sediment heavily impacted by a multitude of contaminants, which is often the case in many developing countries