SSStttooonnnyyy BBBrrrooooookkk UUUnnniiivvveeerrrsssiiitttyyy The official electronic file of this thesis or dissertation is maintained by the University Libraries on behalf of The Graduate School at Stony Brook University. ©©© AAAllllll RRRiiiggghhhtttsss RRReeessseeerrrvvveeeddd bbbyyy AAAuuuttthhhooorrr... Quaternary ammonium compounds (QACs) in marine sediments: detection, occurrence, and application as geochemical tracer A Dissertation Presented By Xiaolin Li to The Graduate School In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Marine and Atmospheric Science Stony Brook University May 2009 Stony Brook University The Graduate School Xiaolin Li We, the dissertation committee for the above candidate for the Doctor of Philosophy degree, hereby recommend acceptance of this dissertation. Bruce J. Brownawell, Dissertation Advisor Associate Professor, School of Marine and Atmospheric Sciences Robert M. Cerrato, Chair of the Defense Associate Professor, School of Marine and Atmospheric Sciences J. Kirk Cochran Professor, School of Marine and Atmospheric Sciences Richard F. Bopp Associate Professor, Rensselaer Polytechnic Institute P. Lee Ferguson Assistant Professor, University of South Carolina This dissertation is accepted by the Graduate School Lawrence Martin Dean of the Graduate School ii Abstract of the dissertation Quaternary ammonium compounds (QACs) in marine sediments: detection, occurrence, and application as geochemical tracer by Xiaolin Li Doctor of Philosophy in Marine and Atmospheric Science Stony Brook Uniersity 2009 Quaternary ammonium compounds (QACs) are a major class of cationic surfactants and have been wildly used in commercial products. However, there is very little knowledge of their environmental sources and fates. This thesis mainly focused on developing robust methods to detect QACs in marine sediments, then studying their occurrence, fate, and application as wastewater-specific tracers of other contaminants in estuarine systems. The study area included large regions of the lower Hudson Basin, iii especially the highly urbanized and sewage affected New York/New Jersey Harbor complex. A robust analytical method was developed using HPLC-MS detection with electrospray (ESI) and Time-of Flight (ToF) detection. Analytical methods were developed with superior extraction efficiency, analyte recoveries and sensitivity than prior approaches. The HPLC-ESI-ToF-MS method was sensitive for all targeted QACs, which included dialkyldimethylammonium compounds (DADMACs), benzalkonium compounds (BACs), and alkyltrimethylammonium compounds (ATMACs). A number of QACs were detected for the first time in environmental samples (e.g., DADMAC C8:C8 and C8:C10), and other high concentration QACs that have not been reported in the scientific literature to date (ATMAC 20 and 22). The specificity of alkylammonium ion detection proved to be surprisingly great. A unique positive mass defect of quaternary ammonium ions was discovered and provides significant resolving power when utilizing ToF or other higher resolution mass spectrometers. This thesis provides the first extensive study of major QACs in any sedimentary environments. QACs are found to be ubiquitous in the NY/NJ Harbor complex with extraordinary high level in the sediments impacted mainly by the wastewater from municipal wastewater treatment plants (WWTP) and combined sewer overflows (CSO). Ditallowdimethylammonium compounds (DTDMAC) are DADMACs with longer alkylchains (C14-C18), and are consistently seen to be the most important QACs in sediments of the lower Hudson Basin. However, more soluble QACs are found to be more abundant in the samples impacted by less treated wastewaters coming from CSOs. Further evidence shows that the extent of biodegradation of QACs during treatment in WWTP positively correlates with the solubility of the compounds, but multiple lines of evidence suggest that all of the QACs studied are preserved well in muddy sediments after they are discharged into the environment. The geochronology of QACs was determined in dated sediment cores and time series surface sediments collected from WWTP-affected areas of the Harbor complex. iv Preservation of all major QACs was further indicated by comparison of matched sediment cores collected 8 years apart. Different classes of QACs, including ATMAC16- 18, ATMAC22, DADMAC C8:C8 to C10:C10, BAC 12-18, and DTDMAC, were characterized by different time histories, which generally agreed well among sites and were in agreement with what little is known about the history of sales and uses of these chemicals. ATMAC22 is reported here for the first time with exponential increases in concentrations over the last 30 years. The potential application of the ATMAC22/ATMAC18 ratio as a highly time-sensitive marker of sewage affected sediment age was demonstrated, providing a good prediction of the time of sewage sludge dumping in sediments collected from the former deep water sewage sludge disposal site, 106 miles off the shore of New Jersey DTDMAC was applied as sewagesource-specific tracer for the source and fate study of three major endocrine disrupting compounds – PCB, PBDE, and NPEO metabolites. Uncharacterized industrial sources for PBDE from upstream Hudson River and Passaic River are separated from the sewage inputs at lower Hudson River by the PBDE congener composition and confirmed by the relationship between sediment concentrations of PBDEs and DTDMAC. A comparison between DTDMAC and different PCB homolog series indicates that the relative importance of upper River sources of PCBs to New York Harbor have continued to decline since the mid 1970s, when serious contamination from two General Electric factories was greatly reduced. While upstream Hudson River sources of lower chlorinated PCBs are still seen in sediments collected in the lower Hudson River between 1998 and 2005, the distributions of all PCB homologs, especially higher chlorinated congeners, has become dominated by urban harbor sources. Throughout the lower Hudson Basin, there was strong correlation between NPEO and DTDMAC levels in sediments collected in the highly depositional sedimentary environment, indicating a common sewage derived source well preserved at those sites. However, in Jamaica Bay sediments, relative depletion of NPEOs and steroid estrogens were observed due to less association of these compounds with suspended particles and sediments that may result in preferential solubilization or microbial degradation. v TABLE AND CONTENTS LIST OF ABBREVIATIONS .................................................................................................................... IX LIST OF FIGURES ..................................................................................................................................... X ACKNOWLEDGEMENTS ...................................................................................................................... XV CHAPTER ONE: INTRODUCTION .......................................................................................................... 1 1.1 WHAT ARE QACS? .............................................................................................................................. 2 1.2 OCCURRENCE OF QACS IN WWTP AND AQUATIC ECOSYSTEMS ...................................................... 5 1.3 AQUATIC TOXICITY OF QACS ............................................................................................................. 6 1.4 BEHAVIOR AND FATE OF QACS IN THE ENVIRONMENT ...................................................................... 8 1.5 ORGANIC CONTAMINANTS AS MOLECULAR TRACERS IN ENVIRONMENTAL GEOCHEMISTRY ......... 11 1.6 ANALYSIS OF QACS IN SEDIMENTS AND SEWAGE SLUDGES ............................................................ 14 1.6.1 Separation and identification of QAC homologues .................................................................. 14 1.6.2 Extraction methods for QACs .................................................................................................... 16 1.7 QACS AS TRACERS OF THE RELATIVE SOURCES AND FATE OF OTHER PARTICLE REACTIVE CONTAMINANTS OF CONCERN IN THE LOWER HUDSON BASIN ............................................................... 17 1.8 NONYLPHENOL POLYETHOXYLATES (NPEOS) AND THEIR NEUTRAL METABOLITES: APPLICATIONS AS BIOGEOCHEMICAL TRACERS, AND SOURCES AND FATE IN THE LOWER HUDSON BASIN .................. 20 1.9 STUDY AREA: SEDIMENTS FROM THE LOWER HUDSON BASIN ......................................................... 22 1.10 OBJECTIVES AND OUTLINE OF THE THESIS ..................................................................................... 24 REFERENCE: .............................................................................................................................................. 26 CHAPTER TWO: ANALYSIS OF QUATERNARY AMMONIUM COMPOUNDS IN ESTUARINE SEDIMENTS BY LC-TOF-MS: VERY HIGH POSITIVE MASS DEFECTS OF ALKYLAMINE IONS PROVIDE POWERFUL DIAGNOSTIC TOOLS FOR IDENTIFICATION AND STRUCTURAL ELUCIDATION .............................................................................................................. 38 2.1 ABSTRACT .......................................................................................................................................... 38 2.2 INTRODUCTION .................................................................................................................................. 38 2.3 EXPERIMENTAL SECTION ..................................................................................................................