4. Environmental Contamination Sensor Development and Evaluations Associated with Natural Disasters; NSF and the Center for Optical Sensors and Spectroscopies (COSS), University of Alabama at Birmingham, 2008 – 2014 The mission of the Center for Optical Sensors and Spectroscopies (COSS) is to promote optical sensing and spectroscopy research on environmental, biomedical, and national security issues through collaborative use of resources and expertise among the member universities, government and industrial laboratories, and improve sensor techniques using recently developed revolutionary laser and spectroscopic technologies. The Deep Water Horizon oil spill off of the southeast coast affecting LA, MS, AL, and FL has highlighted the critical need for rapid environmental monitoring of hazardous wastes and other pollutants. In the last year, COSS environmental researchers associated with the Environmental Institute at UA have been developing and testing methods that can be used to rapidly detect the extent of contamination of spills and discharges of hazardous organic compounds. This work is also investigating the problems associated with the aftermath of these accidents such as determining the potential hazards to responders and residents of the affected areas. Long-term potential contamination of aquatic organisms and the food supply is also of concern that can be better examined using the newly developed methods. The COSS laser-based “optical nose” being developed as part of this NSFsupported research will enable rapid and sensitive measurements of these compounds during, and after, these types of environmental disasters. Our on-going research as part of our COSS activities has been to investigate the sources, fate, and treatment of toxicants, including organic contaminants of most interest to the COSS laser facility. We focused on a wide range of materials, from PAHs and other petroleum hydrocarbons, to heavy metals, and radioactive materials. The work with the organic compounds will enable us to develop and test analytical methods that can be used in times of environmental disasters or homeland security incidents, specifically to obtain rapid data that is currently not available. We initiated this research direction in the aftermath of several severe hurricanes in the gulf coast a few years ago. The unfortunate major oil spill in the gulf is another example of the dramatic need for rapid and reliable information. 4.1 PAHs in Urban Stream Sediments We are also working with Miles College in Birmingham to develop methods using their HPLC and GC/MS equipment to simultaneously quantify the organic compounds that we are investigating during our exposure experiments. Exposure experiments examined the releases of toxic PAH compounds from different asphalt mixtures during the first several months of use, the period when we expect most of these releases to occur. Fate modeling of the organic compounds of interest is used to identify which are likely to cause the most harmful effects, and which can be treated by conventional and advanced wastewater and water treatment methods. The fate of discharged or spilled contaminants was also investigated using fugacity modeling verified by field investigations. 99.9 99 95 90 Percent 80 70 60 50 40 30 20 10 5 1 0.1 0 3 6 9 12 Effect Effects and interactions on Nystatin migration in vadose zone (rainfall and intrinsic permeability most significant, interacting together and separately) HPLC at Miles College used to quantify emerging organic contaminants 3 1.112 1.585 2 1 2 3 4 5 6 7 mVolts 1.586 2.262 1 0 0.000 0.000 0.000 0.000 0.000 0.000 Benzo[g,h,i]perylene 1.827 2.606 Dibenzo[a,h]anthracene 0.000 0.000 Indeno[1,2,3-c,d]pyrene (Benzo[a]pyrene) 0.000 0.000 Benzo[b]fluoranthene Benzo[k]fluoranthene 2.455 3.501 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Chrysene 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Fluoranthene 0.000 0.000 0.0000.000 0.0000.000 0.000 0.000 -3 1.395 1.989 0.000 0.000 Pyrene 3.177 4.530 0.000 0.000 0.000 0.000 1.082 1.542 1.747 2.491 Anthracene 0.969 1.382 0.783 1.116 Flourene -2 0.000 0.000 Acenaphthene 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Naphthalene 0.000 0.000 0.000 0.000 -1 0.000 0.000 0.000 0.000 0.000 0.000 0.208 0.297 Acenaphthylene 0 4.505 6.424 1.590BDL 0.000 1.115 BDL 0.000 mVolts 0.000 0.000 1 0.000 0.000 2 4 Benz[a]anthracene Phenanthrene 0.000 0.000 0.000 0.000 3 10.597 15.113 Nam e EST D concentrati on NORM concentrati on 37.564 53.570 FID PAHStd09290320A 4 -1 -2 -3 8 9 10 11 12 Minutes GC/MSD chromatograph showing large concentrations of several compounds of interest (especially phenanthrene, benz[a]anthracene, indeno[1,2,3-c,d]pyrene, and dibenzo[a,h]anthracene). COSS (the Center for Optical Sensors and Spectroscopies, http://www.coss.phy.uab.edu/) is a multiinstitutional research center located in the Physics Department at the University of Alabama at Birmingham and is supported by NSF EPSCoR. COSS is a group of researchers and facilities from UAB, UA, and UAH. It has two major groups: a) the environmental group headed by Robert Pitt of the Department of Civil, Construction, and Environmental Engineering at UA; b) the laser, sensor, and spectroscopy group headed by Chris Lawson (UAB) and Sergey Mirov (UAB) and Richard Fork (UAH). The mission of COSS is to promote optical sensing and spectroscopy research on environmental, biomedical, and national security issues among the member universities, government and industrial laboratories. One of the primary objectives of COSS is to develop novel optical sensing techniques for detection of hazardous agents, as well as techniques to protect sensors from terrorism-related threats. 13 The main objectives of the environmental research group at UA are: - to identify toxic and hazardous materials and their sampling and measurement methods. with emphasis on heavy metals and organic toxicants, - to use predictive methods to identify the needed measurement levels for extremely hazardous materials for a variety of typical release conditions, - to quantify performance levels for newly developed instruments for different applications, - to verify the performance of new instrumentation and supply quality assurance and quality control, and - to conduct field investigations to quantify fate mechanisms of released toxic and hazardous materials. After reviewing several hundred case histories involving accidental losses of toxic and hazardous materials and other sources, the research team has identified herbicides, pesticides, and PAHs (polycyclic aromatic hydrocarbons) of interest in relationship to environmental monitoring needs, transportation accident hazardous material releases, Water Sentinel water system safety monitoring, and losses during large-scale natural disasters. In order to determine the forms of these compounds that should be monitored, the research team modeled the fate of these compounds to identify the environmental characteristics and chemical factors that may affect their fate when they released into the environment. As part of this study, the team used fugacity calculations to quantify the amount of contaminates partitioned into air, water and solid components of the environment. Factorial design calculations were used to estimate the effects of different factors namely, concentration of contaminant, volume of solids, and organic fraction of solid components on the partitioning of the contaminants. Factorial calculations were used to find the effects of the factors, both individually and their interactions, on their fates. Results clearly showed that the factors of most significance influencing the partitioning of the contaminants onto suspended solids were the concentration of the contaminant, the concentration of suspended solids, and their interaction. The majority of many of these compounds are strongly associated with the particulate matter in the water. Traditional extraction methods needed before sample analysis [solid-phase extraction (SPE) (EPA method 3535, SW-846); continuous extraction of liquid samples (EPA method 3520); Soxhlet (EPA method 3540); automatic Soxhlet method (EPA method 3550, SW-848)] are all problematic in that some have great interferences with the solids in the water, take long times, and require large quantities of dangerous solvents. New procedures that can directly measure these organic compounds at low concentrations would be a great help in rapid response to accidental releases of these compounds. The laser methods being developed by COSS are intended to overcome these problems. After reviewing the different procedures for contaminant preparation and analyses, and based on estimation calculations performed by the research team, the team decided to modify and test a newly developed extraction procedure for the QA/QC analyses. In selecting, modifying, and testing this procedure, importance was given to factors which produce the most reliable results considering the wide range of dissolved and particulate concentrations of the contaminants and relatively rapid methods that use minimal solvents. The selected analytical steps are as follows: filtration of sample to separate the particulates from the dissolved fraction, Solid Phase Extraction of the dissolved fraction, and thermal desorption for the extraction of the solids materials captured on the filter.. Schematic of packed desorption tube (Source: SIS product manual) Model Predicted PAH partition values PAH Naphthalene Anthracene Fluorene Fluoranthene Pyrene Chrysene Benzo(a)anthracene Benzo(b)fluoranthene Dibenzo(a,h)anthracene Indeno(1,2,3-cd)pyrene Benzo(ghi)perylene 24 factorial design (Box, et al 1978) % Partition into Water Suspended Solids Sediment 93 59 74 35 35 9 5 4 1 1 1 0 1 1 2 2 3 3 3 3 3 3 7 40 26 63 63 88 92 94 96 96 96 Probability plot to identify important factors affecting anthracene partition into water and suspended sediment phases respectively Desorption time versus peak areas for pyrene and benzo(ghi)perylene respectively SIS AutoDesorbTM unit Stainless steel Thermal Desorption tubes used for loading samples Tubes and needles conditioning oven Schematic of organic analysis using GC Sampling at Lake Tuscaloosa Sampling point on concrete channel along Cribb’s Mill Creek, Tuscaloosa Sediment sampling along the Carroll’s Creek, Northport Mr. Jejal Bathi operating TD/GC/MS in the laboratory 4.2 PAH Contamination from Newly Paved Surfaces These tests were performed under actual environmental conditions to examine the organic and heavy metal content of runoff from newly installed asphalt pavements and to observe changes in their concentrations with aging during the first several months of exposure. During the life of a pavement, it undergoes aging and hardening due to exposure to temperature, air, and moisture in the environment. This results in the loss of some pavement components by volatilization and irreversible changes in composition by reaction with atmospheric oxygen. Asphalt contains PAHs and heavy metals that represent potential contaminants in water runoff. In addition to PAHs and metals, nutrients, other organic and inorganic toxicants also leach into the runoff when rain water comes in contact with the pavement surface. This study focused on the changes in leaching of these compounds (PAHs, the heavy metals Cd, Cr, Cu, Pb and Zn, and selected nutrients and toxicity) of the runoff from the pavement during initial pavement aging, a period when the most rapid changes occur, and when the runoff is expected to be the most toxic. As part of this effort, we acquired a scanning FTIR spectrophotometer and developed methods to obtain analytical spectra in the range of interest to the COSS laser instrumentation during exposure experiments to quantify losses of critical organic contaminants to the environment, and several very successful outreach activities conducted in conjunction with other NSF projects. The most common IR wavelengths used for analytical purposes for the organic compounds of interest fall outside of the 2 µm (5,000 cm-1) to 3.6 µm (2,800 cm-1) operational range of infrared laser instrumentation. Secondary wavelengths exist in this range, but have not been well documented in the literature. Most of the compounds investigated during the method development phase involved solvents, as shown below for MEK. Research was expended to investigate heavier hydrocarbons and crude oil. Perkin Elmer Spectrum Rx 1 scanning FTIR FTIR scan of Methyl Ethyl Ketone in the range of 2000 to 4500 cm-1 4.3 Heavy Metal Releases from Alternative Drainage System Components The goal of this research is to determine: (1) how contaminants in pipe materials affected the quality of the water and to identify the environmental parameters causing degradation of the material, contact time, and interactions of these factors, and (2) contributions of roof runoff contamination caused by atmospheric deposition. The contaminants being studied include heavy metals, toxicity, nitrates, and phosphates. Prior research has been performed on the contributions of rooftop material to runoff water quality. Results show that the roof runoff quality is dependent on the type of roofing materials used. Little data is available to indicate how piping materials and environmental parameters influence storm water quality. This on-going research is investigating long-term leaching of these compounds from several gutter materials (galvanized aluminum, vinyl, copper, and galvanized steel) and pipe materials (concrete, high-density polyethylene, poly vinyl chloride, and galvanized corrugated steel). Full-sized samples of these materials are being soaked in buffered low and high pH test solutions, at high and low conductivity, with water samples withdrawn every few days for analyses. Copper roof drains and downspouts Vinyl roof drains and downspouts Concrete is the most common currently used piping material Total zinc concentrations in containers with river water. 4.4 Urban Wildlife Bacteria Sources and Survival in the Environment As noted above, additional research tasks during this emerging contaminant project are examining sources and movement of urban area bacteria. Sewage-borne pathogen contamination of urban receiving waters constitutes risk to health. Risks have traditionally been evaluated on the basis of indicator species, microorganisms assumed to have come from sanitary-sewage contamination of the watershed and assumed to indicate the presence of sewage-borne pathogens. Sources other than sewage (e.g., animal feces and soil storage) also contribute to indicator-species assemblages in urban runoff. Accurate assessment of health risk from runoff requires knowledge of these other sources. This research component is analyzing the non-sewage components of microbial indicator species from source areas of various land uses, the potential for mobilization of those species into sheetflow by rainfall, and the particle/surface associations likely to affect transport of those species through the watershed. Survival of E. coli under varying environmental conditions. Warm, wet, and dark conditions allow the bacteria to thrive compared to other conditions which result in much greater reductions of their populations.