With the phaseout of perfluorooctane sulfonate (PFOS) production in most countries and its well known recalcitrance, there is a need to quantify the potential release of PFOS from precursors previously or currently being emitted into the environment. Aerobic biodegradation of N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE) was monitored in two soils from Indiana, USA: an acidic forest silt loam (FRST-48, pH = 5.5) and a high pH agricultural loam (PSF-49, pH = 7.8) with similar organic carbon contents (2.4 and 2.6%) for 210 d and 180 d, respectively. At designated times, triplicate samples were sacrificed for which headspace samples were taken followed by three sequential extractions. Extracts were analyzed using HPLC-tandem mass spectrometry. Measured profiles of EtFOSE degradation and generation/degradation of subsequent metabolites were fitted to the Indiana soils data as well as to a previously published data set for a Canadian soil using an R-based model (KinGUII) to explore pathways and estimate half-lives (t1/2) for EtFOSE and metabolites. EtFOSE degradation ranged from a few days to up to a month. PFOS yields ranged form 1.06–5.49 mol% with the alkaline soils being four to five times higher than the acidic soil. In addition, a direct pathway to PFOS had to be invoked to describe the early generation of PFOS in the Canadian soil. Of all metabolites, the sulfonamidoacetic acids were the most persistent (t1/2 ≥ 3 months) in all soils. We hypothesized that while pH-pKa dependent speciation may have impacted rates, differences in microbial communities between the 3 soils arising from varied soil properties including pH, nutrient levels, soil management, and climatic regions are likely the major factors affecting pathways, rates, and PFOS yields.

More than 2300 sediment pore water distribution coefficients (KPCBi ds) of 93 polychlorinated biphenyls (PCBs) were measured and modeled from sediments from Indiana Harbor and Ship Canal. KPCBi ds were calculated from previously reported bulk sediment values and newly analyzed pore water. PCBs in pore waters were measured using SPME PDMS-fiber and ∑PCB ranged from 41 to 1500 ng L−1. The resulting KPCBi ds were ∼1 log unit lower in comparison to other reported values. A simple model for the KPCBi d consisted of the product of the organic carbon fraction and the octanol–water partition coefficient and provided an excellent prediction for the measured values, with a mean square error of 0.09 ± 0.06. Although black carbon content is very high in these sediments and was expected to play an important role in the distribution of PCBs, no improvement was obtained when a two-carbon model was used.

Over the past decade, studies have shown that exposure to endocrine disrupting chemicals (EDCs) can cause gonadal intersex in fish. Smallmouth bass (Micropterus dolomieu) males appear to be highly susceptible to developing testicular oocytes (TO), the most prevalent form of gonadal intersex, as observed in various areas across the U.S. In this study, prevalence and severity of TO was quantified for smallmouth bass sampled from the St. Joseph River in northern Indiana, intersex biomarkers were developed, and association between TO prevalence and organic contaminants were explored. At some sites, TO prevalence reached maximum levels before decreasing significantly after the spawning season. We examined the relationship between TO presence and expression of gonadal and liver genes involved in sex differentiation and reproductive functions (esr1, esr2, foxl2, fshr, cyp19a, star, lhr and vtg). We found that vitellogenin (vtg) transcript levels were significantly higher in the liver of males with TO, but only when sampled during the spawning season. Further, we identified a positive correlation between plasma VTG levels and vtg transcript levels, suggesting its use as a non-destructive biomarker of intersex in this species. Finally, we evaluated 43 contaminants in surface water at representative sites using passive sampling to look for contaminants with possible links to the observed intersex prevalence. No quantifiable levels of estrogens or other commonly agreed upon EDCs such as the bisphenols were observed in our contaminant assessment; however, we did find high levels of herbicides as well as consistent quantifiable levels of PFOS, PFOA, and triclosan in the watershed where high TO prevalence was exhibited. Our findings suggest that the observed TO prevalence may be the result of exposures to mixtures of nonsteroidal EDCs.

Solid-phase microextraction coupled with gas chromatography-mass spectrometry (SPME-GC-MS) was used to analyze two triazine (atrazine and simazine) and three chloroacetamide herbicides (acetochlor, alachlor, and metolachlor) in water samples from a midwest US agricultural drainage ditch for two growing seasons. The effects of salt concentration, sample volume, extraction time, and injection time on extraction efficiency using a 100-μm polydimethylsiloxane-coated fiber were investigated. By optimizing these parameters, ditch water detection limits of 0.5 μg L-1 simazine and 0.25 μg L-1 atrazine, acetochlor, alachlor, and metolachlor were achieved. The optimum salt concentration was found to be 83% NaCl, while sample volume (10 or 20 mL) negligibly affected analyte peak areas. The optimum extraction time was 40 min, and the optimum injection time was 15 min. Results indicated that atrazine levels in the ditch water exceeded the US maximum contaminant level for drinking water 12% of the time, and atrazine was the most frequently detected among studied analytes. Solid-phase microextraction methods were successfully developed to quantify low levels of herbicides in tile-fed drain water by gas chromatography-mass spectrometry.

Atmospheric nucleation is now recognized to be an important source of ambient particles. In this study, ground–based measurements using a tower were used to observe new particle formation in the Morgan Monroe State Forest (MMSF) in Southwestern Indiana in May 2008. Nucleation was observed at MMSF on a number of days through examination of the particle size distributions. Most of these events were nucleation and growth events that are typical of regional nucleation phenomena. The particle size and sulfuric acid concentration data were used to investigate the mechanism for the observed nucleation events. Four of the ten observed nucleation events were clearly the result of activation of pre–existing clusters. The others seem likely to be the result of classical ternary nucleation.

Under various abiotic stresses, plants overproduce reactive oxygen species (ROS) such as superoxide anion (O₂•⁻), hydroxyl radical (OH•), and hydrogen peroxide (H₂O₂). When in excess, these highly reactive molecules cause oxidative stress, thus damaging proteins, lipids, and DNA. Therefore, plants evolved an enzymatic defense machinery that involves such enzymes as superoxide dismutase (SOD), catalase (CAT), and ascorbate peroxidase (APOX). Various plant families, species and even specimens differ in their ability to withstand the abiotic stress. A study has been undertaken to assess the differences in response to trace metals between two species: a resistant hyperaccumulator Indiana mustard (Brassica juncea) and a metal-sensitive pea (Pisum sativum). We observed that trace elements (Cu, Zn, Cd, Pb) changed the activity of antioxidative enzymes (SOD, APOX, CAT) and the rate of ROS generation. However, in the control plants and at a point 0′ of the treatment, we have noticed a large disproportion in the hydrogen peroxide level, with B. juncea maintaining naturally higher H₂O₂level (up to 40 times higher). We believe that this may be a distinguishing trait common to plants being resistant to oxidative stress.

The connection between nutrient input and algal blooms for inland water productivity is well known but not the spatial pattern of water nutrient loading and algae concentration. Remote sensing provides an effective tool to monitor nutrient abundances via the association with algae concentration. Twenty-one field campaigns have been conducted with samples collected under a diverse range of algal bloom conditions for three central Indiana drinking water bodies, e.g., Eagle Creek Reservoir (ECR), Geist Reservoir (GR), and Morse Reservoir (MR) in 2005, 2006, and 2008, which are strongly influenced anthropogenic activities. Total phosphorus (TP) was estimated through hyperspectral remote sensing due to its close association with chlorophyll a (Chl-a), total suspended matter, Secchi disk transparency (SDT), and turbidity. Correlation analysis was performed to determine sensitive spectral variables for TP, Chl-a, and SDT. A hybrid model combining genetic algorithms and partial least square (GA-PLS) was established for remote estimation of TP, Chl-a, and SDT with selected sensitive spectral variables. The result indicates that TP has close association with diagnostic spectral variables with R 2 ranging from 0.55 to 0.72. However, GA-PLS has better performance with an average R 2 of 0.87 for aggregated dataset. GA-PLS was applied to the airborne imaging data (AISA) to map spatial distribution of TP, Chl-a, and SDT for MR and GR. The eutrophic status was evaluated with Carlson trophic state index using TP, Chl-a, and SDT maps derived from AISA images. Mapping results indicated that most MR belongs to mesotrophic (48.6%) and eutrophic (32.7%), while the situation was more severe for GR with 57.8% belongs to eutrophic class, and more than 40% to hypereutrophic class due to the high turbidity resulting from dredging practices.

Ground-level concentrations of three atmospheric mercury species were measured using manual sampling and analysis to provide data for estimates of mercury dry deposition. Three monitoring stations were operated simultaneously during winter, spring, and summer 2004, adjacent to three mercury wet-deposition monitoring stations in northern, central, and southern Indiana. The monitoring locations differed in land-use setting and annual mercury-emissions level from nearby sources. A timer-controlled air-sampling system that contained a three-part sampling train was used to isolate reactive gaseous mercury, particulate-bound mercury, and elemental mercury. The sampling trains were exchanged every 6 days, and the mercury species were quantified in a laboratory. A quality-assurance study indicated the sampling trains could be held at least 120 h without a significant change in reactive gaseous or particulate-bound mercury concentrations. The manual sampling method was able to provide valid mercury concentrations in 90 to 95% of samples. Statistical differences in mercury concentrations were observed during the project. Concentrations of reactive gaseous and elemental mercury were higher in the daytime samples than in the nighttime samples. Concentrations of reactive gaseous mercury were higher in winter than in summer and were highest at the urban monitoring location. The results of this case study indicated manual sampling and analysis could be a reliable method for measurement of atmospheric mercury species and has the capability for supplying representative concentrations in an effective manner from a long-term deposition-monitoring network.

The global cycle of mercury (Hg) is reasonably well-understood, as are some of the natural and anthropogenic sources of Hg to the atmosphere. Less well understood are the regional and local characteristics of Hg deposition and subsequent watershed-scale transport, important parameters for assessing human risk to various avenues of Hg exposure. This study employed a two-part strategy for understanding coupled deposition and transport processes in central Indiana (USA), including Indianapolis, a typical large city with multiple coal-fired electric utilities and other Hg emission sources. A spatial analysis of Hg concentrations in surface soils revealed elevated Hg proximal to many of the large emission sources, with a distribution aligned along a southwest-northeast axis corresponding to the mean wind direction in this region. This soil distribution suggests some local depositional impact from local utilities, with wind modification affecting the regional pattern. Post-depositional transport of Hg was assessed using a series of streambank sampling arrays as the White River and various tributaries travelled through the urban core of Indianapolis. Streambank sediments had peak Hg concentrations in the urban core, where several local sources are present and where a number of subwatersheds join the main trunk of the White River, suggesting local emission and/or rapid Hg transport from urban subwatersheds due to their relatively high proportion of impervious surfaces. High Hg values persist in White River sediments into rural areas tens of kilometers south of Indianapolis, raising concerns for anglers collecting fish in this apparently “pristine” environment.