Non-regulated organic compounds in Florida sediments

Wat. Res. Vol. 27, No. I 1 pp. 1601-1613, 1993 Printed in Great Britain.All rights reserved

0043-1354/93 $6.00+ 0.00 Copyright © 1993 PergamonPress Ltd

N O N - R E G U L A T E D ORGANIC COMPOUNDS IN F L O R I D A SEDIMENTS K. LIZANNEGARCIAl, JOSEPH J. DELFINO1. and DAVXDH. POWELL2 ~Department of Environmental Engineering Sciences and ~Department of Chemistry, University of Florida, Gainesville, FL 32611, U.S.A. (First received November 1992; accepted in revised form March 1993)

Abstract--Sediment sample extracts initially analyzed by gas chromatography/mass spectrometry during a state-wide study of organic priority pollutants, were re-evaluated using a broad spectrum approach. Mass spectra for most of the non-regulated organic compounds present in each sediment sample extract were screened. Mass spectral data for these non-regulated organic compounds were organized into a spreadsheet database. The non-regulated organic compounds in the database were prioritized and fifteeen of the most frequently occurring compounds or compound groups were chosen for further study and potential identification. Four compounds, calamenene, dehydroabietine, retene and benzo(b)naphtho(2,1d)thiophene were positively identified. Tetrahydroretene was tentatively identified while three compounds remain unidentified. Seven compound groups, including alkylbenzenes, alkylphenols and polycyclic aromatic hydrocarbons (PAHs) contained many isomers so complete identification of the individual isomers within each group was not attempted. Information on possible sources and environmental or toxicological impact of these chemicals was obtained from the literature. Key words--sediments, mass spectrometry, terpenes, alkylbenzenes, PAHs, alkylphenols, extraction, nonregulated organic compounds.

INTRODUCTION The analysis of chemicals in environmental samples is necessary to evaluate the impact of anthropogenic activities on the environment (National Academy of Sciences, 1975). The analysis of one class of these chemicals, specifically organic compounds, has been facilitated by the development of computer-aided gas chromatography/mass spectrometry (GC/MS) instrumentation (Finnigan et al., 1979; Keith, 1976). Studies using GC/MS methods to determine the distribution of organic compounds in environmental samples typically apply either a broad spectrum or a target compound approach (Budde and Eichelberger, 1979). Target compound studies have been used to evaluate the concentrations of expected pollutants in environmental samples, to investigate the environmental distribution of a specific class of cbemicals, or to determine the concentrations of regulated pollutants (Adams and Giam, 1984; Jaffe and Hites, 1985; Ogata and Fujisawa, 1990; Smith et al., 1991). Several researchers have used the broad spectrum approach to determine the identities of the many organic compounds present in environmental samples (Jungclaus et al., 1978; Sheldon and Hires, 1978; Elder et al., 1981; Gomez-Belinchon et al., 1991; Clark et al., 1991). Target compound analysis can inadvertently lead to the discovery of unexpected compounds in en*Author to whom all correspondence should be addressed,

vironmental samples (Jensen, 1972; Peterman and Delfino, 1990). However, a broad spectrum approach is usually necessary to assess the distribution of non-regulated or unexpected compounds in environmental samples, since these may often be overlooked in target compound studies. Why investigate the distribution of non-regulated organic compounds (NROCs)? The organic priority pollutants (OPPs) are typical target analytes (Delfino et al., 1991), yet many of these OPP compounds, specifically DDT and the polychlorinated biphenyl compounds (PCBs), are no longer used or produced commercially in the U.S. Additionally, there are thousands of chemicals currently in use which are not listed as OPPs, and as a result, the environmental distribution and impact of these NROCs have not been well documented. Studies that investigated both regulated (OPPs) and NROCs have shown that NROCs occur more frequently in the environment than the OPP analytes (McFall et al., 1985; Clark et al., 1991). We analyzed sediments to determine the environmental distribution of NROCs since they have been reported to act as both sinks and secondary sources for organic and other chemicals (Forstner, 1989; Stemmer et al., 1990). Hundreds of organic chemicals, in addition to the OPPs, have been detected in sediments from waterbodies near urban areas (Malins et al., 1984), and organic chemicals in sediments have been correlated to diseases and tumors in fish (Malins et al., 1984; Fabacber et al., 1991).

1601

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K. LIZANNEGAgCU~et al.

The present study derived from an investigation of the distribution o f Section 307 (a) Federal Clean Water Act OPPs in the waters and sediments near known hazardous waste sites in Florida (Delfino et al., 1991). The study by Delfino et al. (1991) included a variety o f industrially impacted sites where the most frequently occurring class of compounds was the O P P polycyclic aromatric hydrocarbons. Also, metabolites of D D T , and certain PCBs were found at some sites that were generally known or expected to be contaminated by these OPPs. We focus here on the identification o f frequently occurring N R O C s in sediments that had been previously analyzed for OPPs by G C / M S . Our objectives were: to develop an inventory of N R O C s from the sediment M S data files; to identify the frequently occurring N R O C s ; and to provide information, from the literature, regarding the potential impact o f the identified N R O C s on the environment, DESCRIPTION OF STUDY SITES Thirty-one sites throughout the State o f Florida were investigated, and these encompassed both marine and fresh waters. The study sites were on or adjacent to known hazardous waste sites including creosote w o o d treating facilities, pesticide application operations and waters downstream from paper mills and other industrial facilities, The sites are listed in Table 1, along with the sample identification codes while the general location of each site is shown in Fig. 1. The term sampling site refers to the facility of interest (e.g. a chemical company in Orange County, ORA30), while Table 1. Sediment sampling site codes and adjacent waterbodies Site code HIL01 HIL02 HIL03 HIL04 ESC05 ESC06

ESC07 ESC08 PAL09 PALl0 DADII MONI2 DUVI3 DUVI4 DUVI5 DUVI6 PUTI7 SARI 8 CHAI9 LEE20 LEE21 LEE22 PIN23 PIN24 PIN25 PIN26 POL27 COL28 MAR29 ORA30 GUL31

Adjacent waterbody; Florida county Palm River/Tampa bypass canal; Hillsborough Drainageditch; Hiilsborough Tampa bypass canal/SixmileCreek; Hillsborough Old Tampa Bay/drainage ditch; Hillsborough PensacolaBay/Bayou Chico; Escambia Bayou Chico; Escambia

Elevenmile Creek; Escambia Jack's Branch/Perdido River; Escambia West Palm Beach canal; Palm Beach LWDD L-34 and L-35 (drainage canals); Palm Beach Miami River/canal; Dade Key West; Monroe Unnamedcreek to Baldwin Bay swamp; Dural Little SixmileCreek/Ribald River; Dural St Johns River; Dural Deer Creek/St Johns River; Dural Rice Creek/St Johns River; Putnam Drainageditch; Sarasota Peace River; Charlotte Drainageditch; Lee Drainageditch; Lee CaloosahatcheeRiver; Lee Drainageditch; Pinellas Cross Bayou canal/Old Tampa Bay; Pinellas Cross Bayou canal/drainage ditch; Pinellas Booker Creek; Pinellas Drainageditch; Polk Price Creek; Columbia Rowlandand St Lucie Canals; Martin Lake Ellenor; Orange Gulf county canal/St Josephs Bay; Gulf

sampling location refers to a place from which the sample was collected near a particular site (e.g. ORA30-01). Samples from each o f the 31 sites were included in this study. MATERIALS AND METHODS Sample collection and storage Nine surficial sediment samples and one field duplicate sample were collected by ponar dredge (Wildlife Supply Company) or in low water conditions with a stainless steel trowel from the surface waters adjacent to each site. Sediments were mixed well, transported on ice to the laboratory and frozen until extraction. Sediment extraction and cleanup Sediment extractions were performed by a method developed by Marble and Delfino (1988) and US EPA (1986) and modified by Davis et al. (1993). Initially, 30g of wet sediment and 60 g of anhydrous sodium sulfate (Fisher Scientific) were placed into a 250 ml glass centrifuge tube and mixed. Seventy-five ml of acetonitrile (Optima Grade, Fisher Scientific) was added and the sample was again mixed. The sample was sonicated for 3 min (100% power output, pulsed mode, 50% duty cycle; Model W-375 Sonicator Ultrasonic Liquid Processor, Heat Systems Inc.) and then centrifuged for 30 rain at 1000 rpm. The supernatant solvent was decanted from the centrifuge tube into a 250 ml Erlenmeyer flask. The extraction procedure was performed in triplicate. The combined extract (c. 225 ml) was dried over anhydrous sodium sulfate and concentrated to approx. 10 ml using a rotary flash evaporator (Rotavapor RE-I 1, Buchi) with a water bath held between 40 and 50°C. The extract was quantitively transferred to a 15 ml glass graduated centrifuge tube and concentrated to a final volume of 6 ml under a stream of nitrogen gas (N-Evap Model 111, Organomation Associates Inc.). This preliminary sediment extract was centrifuged to separate any remaining particulates prior to sample cleanup. Sample cleanup of the primary extract was performed using I g C-18 solid phase extraction columns (SPE, Part No. P469R, Fisher Scientific Inc.). The SPE columns were loaded with 0.5 g of copper powder (purified electrolytic dust, Fisher Scientific) to remove elemental sulfur from the crude sediment extracts (Ozretich and Sehroeder, 1986). The C-18 columns were conditioned by pulling 6 ml of methanol (Optima Grade, Fisher Scientific Inc.) through the column under vacuum (water aspirator), followed by 6 ml of deionized water. Two ml of primary sediment extract were loaded into the column reservoir and mixed with 4 ml of deionized water. This mixture was drawn through the C-18 column and the column was air-dried under vacuum for 30 min. The non-polar extractable organic compounds were eluted from the C-18 column into a graduated centrifuge tube using 6 ml of a trisolvent mixture containing methylene chloride, hexane and acetonitrile (50:47:3 by volume). After elution from the column, the final sediment extract was concentrated to ! ml under nitrogen and transferred to a crimp sealed vial. The final extract was stored at 4°C prior to analysis by GC/MS. Analysis o f sediment extracts by G C / M S The final sediment extracts were analyzed using a gas chromatograph combined with an ion trap mass spectrometer (Model 8500 GC, Perkin-Elmer; Model ITD, Finnigan Inc.). The ITD was tuned using perfluorotributylamine. Prior to analysis of sample extracts, daily injection standards were analyzed to verify that the GC/ITD system was operating within acceptable quality control limits. Samples were analyzed on the GC/ITD by injecting approx. 2/zl of the final sediment extract into the GC equipped with a capillary column (30 m x 0.32 #m i.d.,

Non-regulated organic compounds

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1 # m film thickness, RX-5, Part No. 10254, Restec Inc.) using the splitless injection mode. The GC oven was programmed as follows: 50°C for 1.5 min, increased at 20°C/rain to 130°C; held at 130°C for 3 rain; increased at 12°C/rain to 180°C; increased at 7°C/rain to 300°C; and finally held at 300°C for 32 min. Electron ionization (70 eV) mass spectra were acquired, in the full scan mode, over a mass range of 45-450 Da, at a rate of two scans per second.

Collection and organization of non-regulated organic cornpound data An inventory of NROCs in the sediment extract data files was compiled by examining each file and recording the NROCs present. Typically, the mass spectrum of a NROC had to have a base peak intensity greater than about 3000 area counts, before information from the NROC mass spectrum was recorded in the NROC inventory. The sample code, scan number, base peak, base peak intensity, the next three most abundant ions and the apparent molecular ion (AMI) were recorded for each NROC mass spectrum. The

AMI was determined by visually examining the NROC spectrum and choosing the m/z value that appeared to represent the molecular ion of the NROC.

Database organization Selected records from a total of over 4000 were entered into a database (dBASE lII PLUS, Ashton Tate, 1985). Compounds that displayed a mass spectrum indicative of aliphatic and alicyclic hydrocarbons (McLafferty, 1980) were excluded due to the lack of definitive information from the electron ionization mass spectra. About 2800 data records remaining in the NROC database represented varipus compounds or classes of compounds, including PAHs and substituted aromatic compounds. Similar spectra in the database were grouped by aid of a computer program. Ultimately, a verification process resuited in the designation of Single Compound Groups and Isomer Groups. Polycyclic aromatic hydrocarbons, substituted PAHs, alkylbenzenes and alkylphenols typically occurred in the sediment extracts as complex mixtures of

K. LIZANNEGARCIA et al.

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Table 2. Fifteen most frequently occurring non-regulated organic compound groups

Compound name or compound class

Number of locations where detected (of 310)

Number of sites where detected (of 31)

91 55 54 48 47 45 43 38 35 33 33 31 29 29 27

19 22 20 16 14 18 13 17 9 II 1l 12 l0 14

Isomers of the PAH w/empirical formula = C20H~z Alkylbenzene compounds I~hydroabietine Isomers of the PAH w/empirical formula = C 17H 12 Unknown w/apparent molecular weight = 292 Tetrahydroretene Retene (7-isopropyl-l -methyl-phenanthrene) Calamenene Saturated hydrocarbon w/apparent molecular weight = 262 Isomers of the PAH w/empirical formula = CI8H~2 Unknown w/apparent molecular weight = 274 Isomers of various alkylpbenol compounds Unknown w/apparent molecular weight = 292 Isomers of methyl anthracene and/or phenanthrene Benzo(b)naphtho(2,l-d)thiophene

15

isomers and these compounds were designated as Isomer Groups. Single compound groups were defined as a group of records with identical spectra and retention times that agreed within + 30 s. Preliminary characterization of the single compound and isomer groups was accomplished by comparing the mass spectral data recorded for the NROCs to mass spectral indices and literature spectra, and by the recognition of spectra representative of a specific compound class, Over 100 groups of compounds were detected during the initial characterization of the non-regulated database. Of those groups, fifty were detected at ten or more locations and these were ranked according to the number of locations where each was detected. Ultimately, the fifteen most frequently occurring NROC groups from the ranked list were chosen for potential identification (Table 2).

extrapolating this confirmation to the remaining samples from the same group. Standards were obtained from the following sources. Retene (Transworld Chemicals) was available from studies performed by Buelow (1982). Benzo(b)naphtho(2,1d)thiophene and dehydroabietine (norabietatriene) were purchased from Aldrich Chemical Company Inc. and Chiron Laboratories Inc., respectively. Calamenene was provided by Dr Mark Whitten (Florida Natural History Museum, Gainesville, Fla) through the courtesy of Dr R. P. Adams (Baylor University, Waco, Tex.).

Non-regulated organic compound identification The confidence level to which the fifteen most frequently occurring compound groups were identified depended on the type of group and the availability of standards. Positive identification of individual compounds within the isomer groups would have required resources beyond the scope of our project, therefore these groups were characterized to the compound class level. Single compound groups were sclected for potential positive identification, Characterization of the isomer groups was done by comparing representative spectra from each Isomer Group to the Eight Peak Index of Mass Spectra (Mass Spectrometry Data Centre, 1974) and to spectra in the EPA /N1H Mass Spectral Data Base (Milne and Heller, 1978, 1980, 1984). If the spectra in an isomer group were visually determined to match spectra of several isomers in these indices, then the matched compounds were noted and the group was characterized, Positive identification was attempted for each of the six single compound groups represented in the 15 most frequently occurring groups. Positive identification of each compound was not always achieved, however a tentative identification was assigned to a single compound group if the mass spectrum of the compound closely resembled a mass spectrum published in the literature but no commercial standard could be obtained, Positive identification of a single compound group was confirmed if the mass spectrum and retention time of the standard (analyzed on the same GC/ITD and at the same operating conditions as the sample extract) matched the mass spectrum and retention time of the tentatively identified compound from a sediment extract. The retention times of the compound in the sediment extract and the standard were required to be within + 15 s for a positive identification to be confirmed. A confirmed identification in at least three sediment sample extracts from a group was required before

The non-regulated organic c o m p o u n d inventory based o n 310 sediment samples from 31 sampling locations (Table 1) indicated t h a t over 100 different compound groups were present in the sediment extracts. Some of the compound groups contained

RESULTS

AND DISCUSSION

Overview

several structural isomers, leading to a n even larger n u m b e r o f N R O C s t h a n were actually detected. This initial data set o f over I00 c o m p o u n d groups conrained m a n y groups o f c o m p o u n d s t h a t occurred at fewer than 10 sampling locations. Fifty non-regulated organic c o m p o u n d groups were detected at ten or m o r e sampling locations, a n d 15 o f these were chosen for potential identification based on the relatively wide statewide distribution o f these c o m p o u n d s . These included isomer groups a n d single c o m p o u n d groups as s h o w n in Table 2, along with the number o f sites where they occurred.

AIkylbenzenes AIkylbenzenes were detected at 22 sites, a n d most o f the sediment samples analyzed c o n t a i n e d a cornplex mixture of alkylbenzene isomers. Several samples exhibited a n apparent homologous series o f C3-C6 alkylbenzenes. Higher molecular weight alkylbenzenes m a y have also been present in the sediment extracts, however, this could n o t be verified by the

electron ionization mass spectra. Lower molecular weight alkylbenzenes (C3-C7) have been reported in sediments ( M a c L e o d et al., 1977), but apparently not as frequently as in other

Non-regulated organic compounds environmental compartments. The C3-C6 alkylbenzenes have been identified in river water (Sheldon and Hites, 1978; Giger et al., 1979; Gomez-Belinchon et al., 1991), lake water (Grob and Grob, 1974), air (Holzer et al., 1977) and in landfill leachate plumes (Reinhard et al., 1984). In general, the environmental occurrence of these lower molecular weight alkylbenzenes has been attributed to fossil fuel and solvent use (GomezBelinchon et al., 1991), as well as wastewater effluents (Eganhouse and Kaplan, 1982a; Clark et al., 1991). Higher molecular weight alkylbenzenes reported in environmental samples are typically C~0-Cj4 monosubstituted benzenes. These long-chain linear alkylbenzenes have been reported in river water (Gomez-Belinchon et al., 1991), marine suspended sediments (Crisp et al., 1979), deposited sediments (Eganhouse et al., 1983; Ishiwatari et al., 1983; Peterman and Delfino, 1990) and fish (Peterman and Delfino, 1990). The occurrence of linear aikylbenzenes in environmental samples usually has been related to linear alkylbenzene sulfonate surfactants used in detergent production that enter surface waters via wastewater effluent discharges (Crisp et al., 1979; Eganhouse and Kaplan, 1982b; Eganhouse et al., 1983; Ishiwatari et al., 1983). However, Peterman and Delfino (1990) detected linear alkylbenzenes (C~0-C~3) in sediment and fish and determined the source of these compounds to be an industrial mixture, Alkylate 215, that was used as a diluent in the production of carbonless copy paper, Low molecular weight alkylbenzenes and linear alkylbenzenes have been detected in fish (Whipple, 1981; Peterman and Delfino, 1990) and in sediments (Takada and Ishiwatari, 1990). The C3 and larger alkylbenzenes show low chronic and acute toxicity to mammals, but like toluene, xylenes and ethylbenzenes, they can cause membrane irritation and central nervous system depression (Fawell and Hunt, 1988).

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well as natural sources from decaying of plant material (Phipps et al., 1981). Nonylphenols have been identified in sewage effluents (Giger et al., 1981; Stephanou and Giger, 1982; Clark et al., 1991), in wastes from a tire manufacturing plant (Junglaus et al., 1978) and a refinery-petrochemical plant (Chriswell et al., 1975). In our study, one of the most likely sources of nonylphenoi in surface waters could be from degradation of nonylphenol ethoxylate surfactants (Stephanou and Giger, 1987; Ankley et al., 1990). Toxicity and other adverse effects of alkylphenols vary with molecular weight and structure. The higher molecular weight alkylphenols (Cs and larger) have been reported to cause skin irritation in guinea pigs (Zavadskii and Khovanova, 1975). The toxicity of various alkylphenols to several aquatic species, ineluding fatbead minnows (Pimephalespromelas), has been shown to increase with increasing molecular weight, and also the structure of the alkyl side chain influences toxicity (McLeese et al., 1981; Phipps et al., 1981; Holcombe et al., 1984). Nonylphenol has been shown to be toxic to Ceriodaphnia dubia (Ankley et al., 1990). Polycyclic aromatic hydrocarbons ( P A H s )

Polycyclic aromatic hydrocarbons with the moiecular formulae C20H~2, CIsHj2, CITHI2, were frequently detected in the sediment extracts, and for the purposes of this study, these groups will be referred to as PAH 252, PAH 228 and PAH 216, respectively. An alkyl-PAH with molecular weight 192 was characterized as methylphenanthrene or methylanthracene, and this group will be referred to as alkyl-PAH 192. Each molecular weight PAH group has the potential to contain several isomers, and in fact, each of the detected PAH groups contained two or more nonregulated isomers. The PAH 252 and PAH 228 groups, in addition to the non-regulated isomers detected, have one or more isomers which are organic priority pollutants. The mass spectra for each of the isomers within a PAH group are almost identical, making even tentative identification of these comAlkylphenols pounds difficult by GC/MS methods alone. Alkylphenois were detected in samples from 12 Polycyclic aromatic hydrocarbons (PAHs) are sites and they usually occurred in the sediments as a probably the most frequently reported organic poilucomplex mixture of isomers. A poorly resolved group tants in sediments and they have been found in of isomers was present in many of the sediment sediments from around the world (Blumer and samples (Fig. 2), and these alkylphenols may be Youngbiood, 1975; LaFlammeand Hites, 1978; Lake components o f a nonylphenolmixture based on their et al., 1979; Hites et al., 1980; Wakeham et al., close correspondence to spectra of nonylphenols 1980a,b; Tan and Heit, 1981; Venkatesan and reported by Giger et al. (1981). Kaplan, 1982; Johnson et al., 1985; Heifrich and Phenolic compounds have been identified in the Armstrong, 1986; Barrick and Prahl, 1987; Bousurface microlayer of a lake (McFall et al., 1977), in loubassi and Saliot, 1991; Jacobs et al., 1993). river water (Sheldon and Hites, 1978), in sediments Polycyclic aromatic hydrocarbons are formed by (Jungclaus et al., 1978) and in samples related to pulp the combustion of organic substances (Blumer, 1976; and paper mill effluents (Peterman et al., 1980). The LaFlamme and Hites, 1978), and can enter the sources of phenolic compounds in surface waters aquatic environment by atmospheric deposition of include wastewater effluents (Giger et al., 1981; airborne particulates formed during the combustion Stephanou and Giger, 1982; Clarke et al., 1991), as process (LaFlamme and Hites, 1978; Tan and Heit,

1606

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1981). The discharge of urban stormwater runoff, which contains PAHs from asphalt and automobile exhaust particles (Wakeham et al., 1980a; Takada et al., 1990), and effluents from combined sewage/ stormwater and municipal treatment plants (Barrick, 1982; Eganhouse and Kaplan, 1982b) have been

related to the occurrence of PAHs in surface waters and sediments. Creosote is a mixture of PAHs and other compounds, and creosote treatment facilities also have been related to PAH contamination of surface waters and associated biota (Rostad and Pereira, 1987).

Non-regulated organic compounds The PAHs found in the sediments during this study likely stem from a combination of the above sources. However, based on the findings of Delfino et al. (1991), and reinforced in this study, the PAHs identified in sediments adjacent to creosote wood treating facilities likely originated from the creosote used on those sites, Polycyclic aromatic hydrocarbons are typically regarded as a class of carcinogenic compounds. However, carcinogenicity and other adverse health effects of PAHs vary with molecular weight and structure (Dipple, 1985). Polycyclic aromatic hydrocarbons have been shown to accumulate in mollusks, fish and other aquatic plants and animals (Eisler, 1987; Hugget et al., 1987; Rostad and Pereira, 1987; DeLeon et aL, 1988).

1607

Terpenes

Several terpenes, with estimated concentrations ranging from 1 to 60/lg/g (dry weight) were detected in many sediment samples. Tetrahydroretene, the second most frequently occurring single compound in the sediment extracts, was tentatively identified in sediment samples from 18 sites in Florida. The spectrum from a sediment extract (Fig. 3) was compared to one of tetrahydroretene reported by Wakeham et aL (1980b) and the sediment extract spectrum possessed the same fragmentation pattern and ion intensities as the tetrahydroretene standard. Therefore a tentative identification was assigned. Dehydroabietine was positively identified at 20 sites statewide. The names dehydroabietine and 18norabieta-8,11,13-triene have been used interchangeably in the literature. Standards of calamenene and Aliphatic hydrocarbons retene were analyzed on our GC/ITD instrument and Aliphatic and alicyclic hydrocarbons occurred in the retention times and mass spectra of these two the majority of the sediment extracts analyzed for this compounds matched the retention times and mass study. However, only one aliphatic hydrocarbon spectra of the two compounds in the sediment group was chosen for further investigation, that being samples. Thus, calamenene and retene were positively a saturated hydrocarbon with a molecular weight identified in sediment samples from 17 and 13 sites, greater than or equal to 262. respectively. Mass spectra for the positively identified Aliphatic hydrocarbons have been identified in terpenes are shown in Fig. 4. sediments (Clark and Blumer, 1967; Farrington and Retene has been reported in marine and aquatic Tripp, 1977; Simoneit, 1977; Bouloubassi and Saliot, sediments worldwide (Wakeham et al., 1980b; Tan 1991), suspended sediments (Crisp et aL, 1979), and Heit, 1981; Venkatesan and Kaplan, 1982; wastewater effluents (Giger et al., 1979; Barrick, 1982; Buelow, 1982; Helfrich and Armstrong, 1986; Barrick Eganhouse and Kaplan, 1982a, b) and in aerosols and Prahl, 1987). Retene has also been identified in (Simoneit and Mazurek, 1982). The principal the wastewaters of an integrated unbleached kraft sources of aliphatic hydrocarbons to aquatic/ pulp and paper mill (Buelow, 1982) and in aerosols marine environments are fossil fuel use and biological over rural forested and desert areas (Simoneit and inputs (Clark and Blumer, 1967; Farrington and Mazurek, 1982; Mazurek et al., 1991). Tripp, 1977), and these are also the most likely Several researchers have identified tetrahysources of the aliphatic hydrocarbons found during droretene, 18-norabieta-8,11,13-triene and calameour study, nene in marine and aquatic sediments (Simoneit et al., Toxicological information on individual aliphatic 1979; Yamaoka, 1979; Wakeham et aL, 1980b; hydrocarbon compounds is limited, although the Buelow, 1982). Simoneit and Mazurek (1982) identinformation available suggests that, in general, all- ified 18-norbieta-8,11,13-triene and calamenene in phatic hydrocarbons have low acute and chronic aerosols over the rural western United States. Tetra toxicities (Faweli and Hunt, 1988). hydroretene, dehydroabietine and calamenene have

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Fig. 4. Mass spectra of tcrpenes positively identified in the sediment extracts: (A) calamenen¢; (B) dehydroabietine; and (C) retene.

also been found in the effluent from pulp and paper mills (Buelow, 1982; Leuenberger et al., 1985). There are several potential sources of retene, and other terpene hydrocarbons, to the environment. Several researchers have concluded that the presence of retene in sediments is due to the in situ degradation of abietic acid, a major component of pine resin (LaFlamme and Hites, 1978; Hites et al., 1980; Wakeham et al., 1980b; Tan and Heit, 1981). According to Wakeham et al. (1980b) and LaFlamme and Hites (1978), the conversion of abietic acid to retene results in several intermediate compounds, including tetrahydroretene and dehydroabietine, both of which were detected in the sediment extracts examined for this study,

A second source of retene, tetrahydroretene, calamenene and dehydrobietine could be related to the discharge of paper mill effluent (Buelow, 1982; Leuenberger et al., 1985). Yet another possible source of these compounds could be atmospheric deposition. Simoneit and Mazurek (1982) and Mazurek et aL (1991) detected retene, calamenene and 18-norabieta8,11,13-triene in aerosols and Ramdahl (1983) identified retene in the emissions from coniferous wood smoke. The sources of terpenes in the sediments examined for this study likely stem from both natural and anthropogenic sources. The degradation of abietic acid could be responsible for the terpenes found in sediments remote from industrial activities. However,

Non-regulated organic compounds the paper mills and wood treating facilities sampled for this study likely acted as substantial localized sources of terpenes. Simoneit and Mazurek (1982) proposed that the presence ofcalamenene in aerosols is due to diagenesis of cadinene and cadinol sesquiterpenes. The biogenic precursors are unstable in the environment and undergo various reactions to form the sesquiterpene hydrocarbons, including calamenene (Simoneit and Mazurek, 1982). Therefore calamenene, like retene, tetrahydroretene and dehydroabietine, is possibly derived from diagenetic processes in the sediments, No literature was found regarding the toxicity and/or the environmental impact of tetrahydroretene, retene, dehydroabietine or calamenene. However, resin acids have been shown to be both acutely and chronically toxic to fish (Leach and Thakore, 1977; Groose, 1982). Several terpenes or mixtures of terpenes have been found to be carcinogenic, mutagenic (Roe and Field, 1965; Gordon et al., 1982; Kurttio et al., 1990) and acutely toxic (MacGregor et al., 1974).

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Little information was found that indicated the possible sources of BNT to the environment. Lee and Hites (1976) indicated that Carbon black, which contains BNT, is used in tire production. Street dust, containing tire wear particles (Takada et al., 1990), could be a major source of BNT to the sediments. Benzonaphthothiophene presumably occurs in the sediments investigated for this study as a result of stormwater runoff and combustion of fossil fuels containing PASHs. There is a paucity of information in the literature regarding the environmental impact of BNT, however other sulfur-containing polycyclic aromatic hydrocarbons (PASHs) have been found to accumulate in biota (Ogata et al., 1980). A study that investigated the mutagenicity of various PASHs, including isomers of BNT reported that benzo(b)naphtbo(2,l-d)thiopbene was the least mutagenic compound tested (Pelroy et al., 1983). Unidentified compounds Three compounds and/or groups of the original set of 15 could not be identified by the methods used in this study. Mass spectra representative of these are shown in Fig. 6. During the course of our study, mass spectra from various literature sources and the most recent indices available to us were continually searched and compared to the mass spectra of the compound groups selected for this study. Several compound groups were successfully identified by this approach, but we could not locate spectra that resembled those in Fig. 6.

Benzonaphthothiophene Benzo(b)naphtho(2,l-d)thiophene (BNT) was confirmed in sediment samples from 15 sites by matching the mass spectrum and retention time of the compound in the sediment sample to the mass spectrum and retention time of a BNT standard that was analyzed on our GC/ITD instrument. The estimated concentrations of BNT in the sediments ranged from <1 to 15/tg/g. The mass spectrum of the BNT identified in the sediment samples is shown in Fig. 5. Benzo(b)naphtho(2,l-d)thiophene has not been widely reported but was found in tributaries to the Great Lakes (Fabacher et al., 1991) while Ogata and Fujisawa (1990)detected other organic sulfur cornpounds, mainly alkyi benzothiophenes, in sediments from industrial ports. Takada et al. (1990) identified BNT as a component of street dusts. Benzonaphthothiophene has also been found in carbon black (Lee and Hites, 1976; Nishioka et al., 1986), coal tar (Nishioka et al., 1986; Yu et al., 1990), in crude oil and in the flue gas of brown coal (Grimmer et al., 1983a, b).

SUMMARY AND CONCLUSIONS The most frequently occurring non-regulated organic compound groups found in the sediment samples from this study included PAHs, alkyl-PAHs, alkylbenzenes, alkylphenols, terpenes and aliphatic hydrocarbons. This study was designed to provide a broad survey of the frequently occurring NROCs in sediments from Florida. It was not designed to specifically determine the specific sources of the cornpounds detected, however most of the compound groups detected in the sediments clearly originate Z34

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m/z Fig. 6. Representative mass spectra of the three compounds or groups that remain unidentified in the sediment extracts. from diverse anthropogenic as well as natural sources, The frequent occurrences of alkylbenzenes and aliphatic hydrocarbons in the sediment sample extracts are likely due to a variety of sources, including fossil fuels and surfactants. Alkylphenols were also detected in many sediment samples from different sites, and they are probably related to the use of detergents. The most common statewide sources of the PAH compounds are presumably due to combustion of fuels and petroleum fuel spills, Several related terpene hydrocarbons were detected in the sediment sample extracts. Dehydroabietine, calamenene and retene were positively identified, and tetrahydroretene was tentatively identified. Sources

of these terpene compounds likely include paper mills and other forest-product related industries, however natural sources, such as runoff from forested areas and deposition of plant material, are also possible. Benzo(b)naphtho(2,1-d)thiophene (BNT), a sulfurcontaining polycyclic aromatic hydrocarbon (PASH), was positively identified in many sediment samples collected in Florida. Tire wear particles present in stormwater runoff and atmospheric deposition of combustion products are possible sources of BNT to the sediments. The organic priority pollutant list does not account for alkylphenols, alkylbenzenes, alkyl-PAHs or terpenes, and therefore the environmental distribution and toxicology of these classes of compounds has not

Non-regulated organic compounds been often reported. Based on this study, we found that alkylbenzenes, alkylphenols and terpenes are widely distributed in Florida sediments and that the

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Toxic pollutants in discharges, ambient waters and bottom sediments. Final Report to Florida Dept. Environ. Reg., University of Florida, Gainesville, Fla. Dipple A. (1985) Polycyclic aromatic hydrocarbons: an environmental impacts and human health effects introduction. In Polycyclic Hydrocarbons and Careinoof these c o m p o u n d classes need to be investigated genesis (Edited by Harvey R. G.), pp. 1-17. American further. Chemical Society, Washington, D.C. Eganhouse R. P. and Kaplan I. R. (1982a) Extractable Acknowledgements--This research was supported, in part, organic matter in municipal wastewaters. 2. Hydrocarby the Florida Department of Environmental Regulation bons: molecular characterization. Envir. Sci. Technol. 16, Contract No. WM266. The project manager was Dean 541-551. Jackman. Assistance in sediment extractions and analyses Eganhouse R. P. and Kaplan I. R. (1982b) Extractable was provided by W. M. Davis, J. A. Coates, L. L. 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