Which Coastal and Marine Environmental Contaminants Are Truly Emerging?

Environ Sci Pollut Res DOI 10.1007/s11356-014-2856-1

DEVELOPMENTS AND APPLICATIONS OF ENVIRONMENTAL SPECIMEN BANKS FOR MONITORING EMERGING CONTAMINANTS

Which coastal and marine environmental contaminants are truly emerging?

Keith A. Maruya & Nathan G. Dodder & Chi-Li Tang & Wenjian Lao & David Tsukada

Received: 26 January 2014 /Accepted: 31 March 2014 # Springer-Verlag Berlin Heidelberg 2014

Abstract To better understand the past and present impact of decreasing in concentration, whereas others (e.g., miconazole, contaminants of emerging concern (CECs) in coastal and triclosan) are increasing. marine ecosystems, archived samples were analyzed for a broad suite of analytes, including pharmaceuticals and per- Keywords Pharmaceutical and personal care products sonal care products (PPCPs), flame retardants (including (PPCPs) . Nonylphenol . Triclosan . Triclocarban . PBDEs), perfluorinated compounds (PFCs), and current-use Polybrominated, diphenyl ethers (PBDEs) . Sediment core . pesticides. Surface sediment, mussels (Mytilus spp.) and sed- Bivalves . Historical input iment core samples collected from the California (USA) coast were obtained from environmental specimen banks. Selected CECs were detected in recent surface sediments, with Introduction nonylphenol (4-NP), its mono- and di-ethoxylates (NP1EO and NP2EO), triclocarban, and pyrethroid insecticides in the After WWII, input of anthropogenic contaminants into the greatest abundance. Alkylphenols, triclocarban, and triclosan coastal zone has focused on trace elements and persistent were present in sediment core segments from the 1970s, as organic pollutants (POPs). As an example of a highly impact- well as in Mytilus tissue collected during the 1990s. Increasing ed coastal urbanized area, the nearshore marine environment concentrations of some CECs (e.g., miconazole, triclosan) off the coast of southern California (USA) has been subject to were observed in the surface layers (ca. 2007) of a sediment loading of DDTs, PCBs, and metals (Cu, Hg, Pb, and Zn). core, in contrast to peak concentrations of 4-NP and This region, home to the marine Superfund site on the Palos triclocarban corresponding to input during the 1970s, and an Verdes shelf established by the U.S. Environmental Protection apparent peak input for PBDEs during the 1990s. These Agency in 1996 (http://www.epa.gov/region09/superfund/ results suggest that chemicals sometimes referred to as pvshelf/), has been monitored on a 5-year cycle for the past “emerging” (e.g., alkylphenols, triclocarban) have been pres- 20 years using a weight of evidence, probabilistic design. ent in the aquatic environment for several decades and are Whereas obvious biological insults (eggshell thinning, fish fin rot) documented in the 1960s to the 1980s have been mitigated (SCCWRP 2012), new concerns over chronic ex- Responsible editor: Hongwen Sun posure have emerged. As a result, management action during the last two decades Electronic supplementary material The online version of this article (doi:10.1007/s11356-014-2856-1) contains supplementary material, has shifted focus from POPs and metals to contaminants of which is available to authorized users. emerging concern (CECs), including pharmaceuticals and personal care products (PPCPs), industrial/commercial prod- K. A. Maruya (*) : N. G. Dodder : W. Lao : D. Tsukada Southern California Coastal Water Research Project Authority, Costa ucts, newly registered pesticides, and even food products. The Mesa, CA 92626, USA mode of action associated with most CECs differs from the e-mail: [email protected] acute effects from the past (Preuss et al. 2006;Ankleyetal. 2008; Drury et al. 2013). One new challenge is to understand C.

Since the advent of and the priority pollutant list, 130 individual substances have been routinely measured in environmental matrices. During the same period of time, however, many other common-use chemicals, e.g., antimicrobials such as triclocarban and alkylphenolic technical mixtures used as surfactants, have gone relatively unmonitored, largely because of their “inertness” to toxicological endpoints such as acute toxicity. For pest control, pyrethroids have replaced organo- phosphates which in turn replaced legacy organochlorine pesticides. In addition, chemical enterprise has introduced thousands, perhaps tens of thousands, of new chemicals over the past 20 years. What is the current chemical exposure in coastal and marine ecosystems? How has that differed from 20 years ago? What future exposure trends can we expect?The answer to these questions will help put the biological re- sponses of the past, present, and future in the proper perspective. The objectives of this study were to compare the historical input and wildlife exposure of non-priority pollutants (i.e., CECs) with current conditions in coastal and marine ecosystems Fig. 1 Archived samples of sediment and mussels (Mytilus spp.) collect- of California and characterize their temporal trend over the past ed during the period 1995–2009 at four locations off the coast of Cali- ≥ 20 years. To achieve this, archived samples of sediment and fornia, USA, were analyzed retrospectively for 150 chemicals of emerg- – ing concern (CECs). Shading indicates regions with population densities bivalve tissue for the period 1995 2009 were analyzed for a >965/km2.Theinset shows the Palos Verdes peninsula where the sedi- broad suite of largely unregulated and unmonitored chemicals. ment core was sampled

operations, and/or large (>50,000 inhabitants) cities. These Materials and methods stations were recently categorized as mixed development (SFSM), urbanized (MDSJ), and undeveloped (SSSS) accord- Study sites ing to adjacent land cover (Maruya et al. 2013a). Moreover, GIS analysis of National Pollutant Discharge Elimination Locally abundant bivalves and surface sediment (top 5 cm) System (NPDES) data layers revealed that SFSM was in have been collected biannually since 1986 at 34 stations along proximity to both WWTP and stormwater runoff discharges, the California coast following protocols established by the MDSJ to stormwater runoff only, and SSSS to neither sources. National Status and Trends Mussel Watch program The Palos Verdes shelf is a relatively narrow, low gradient (Lauenstein et al. 1997; Lauenstein and Cantillo 1998). component of the continental shelf at the margin of the North Archived samples from three historical Mussel Watch stations American continent and the eastern Pacific Ocean near the representing different degrees of human impact were targeted city of Los Angeles (Sherwood et al. 2002). Since 1937, the for the present study (Fig. 1). In southern California, the Sanitation Districts of Los Angeles County (“Sanitation Marina del Rey South Jetty (MDSJ) station is located at the Districts”) have discharged effluent from a WWTP onto the entrance to Marina del Rey, a residential boat basin in Los shelf via one or more submarine outfalls at depths ranging Angeles County that under normal conditions receives no from 30 to 60 m. As a result, sediments in the vicinity of the wastewater treatment plant (WWTP) discharge and is subject outfall became contaminated with metal and organic contam- to runoff from marina and other recreational activities and the inants, including residues from over 800 tons of technical surrounding urban landscape. In San Francisco Bay, the San DDT, some of which remain in shelf sediments (Fernandez Francisco Bay San Mateo Bridge (SFSM) station is located at et al. 2012) discharged between the 1940s and early 1970s. As the foot of the San Mateo Bridge, within 10 km of multiple part of their ocean monitoring program, between 1982 and WWTP outfalls that discharge into the shallow, enclosed arm 2007, the Sanitation Districts collected and analyzed sediment of the estuary that also receives runoff from the surrounding, cores at multiple locations on a biennial basis to track the fate, largely developed watersheds. In contrast, the San Simeon transport, and degradation of DDTs in PV shelf sediments. (SSSS) station near San Simeon on the central coast lies Archived samples of surface sediment and mussel tissue roughly (~300 km) equidistant between the San Francisco (Mytilus spp.) from SFSM, SSSS, and MDSJ were obtained Bay and Los Angeles metropolitan areas, a section of the from the National Oceanic and Atmospheric Administration/ coast that is devoid of heavy industry, large commercial National Institute of Standards and Technology (NOAA/NIST) Environ Sci Pollut Res sample archives located in Charleston, SC, and College Station, concentration; (2) the internal standard recovery for com- TX, USA. Surface sediment collected in 2006 and mussel tissue pounds quantified by isotope dilution methods was 25 to representing a time series (1995 to 2009) were obtained (Online 175 % (for LC-MS/MS analytes); otherwise, the recovery of Resource 1). Homogenized sediment samples representing 2- dibromooctafluorobiphenyl (DBOFB) and PCB-208 spiked cm segments of an intact core, collected at Palos Verdes shelf into each sample prior to extraction was 70 to 130 % (for station 3C (PVS3C) in December 2007 following standardized GC-EI or NCI-MS analytes); and (3) the spiked matrix recov- procedures established by the USEPA, were provided by the ery was 40 to 150 %. Samples of surface sediment, sediment Sanitation Districts. The sediment core location (PVS3C) is core, and mussel tissue were processed separately; therefore, ~10 km northwest of the WWTP submarine outfall (Fig. 1). compounds failing QC (13, 33, and 28, respectively) were After thawing at room temperature, core segment samples removed from the working data set for each of these three were re-homogenized and combined into nine composites categories (Online Resource 5; ESM Fig 2). Blank concentra- representing the following depth segments: (i) 0–4 cm, (ii) tions were subtracted from measured concentrations for target 4–8 cm, (iii) 8–12 cm, (iv) 12–16 cm, (v) 16–20 cm, (vi) 20– CECs which met QA/QC criteria (1) above. 26 cm, (vii) 26–32 cm, (viii) 32–46 cm, and (ix) 46–76 cm; based on segment dating estimated from the peak concentration of p,p′-DDE (Online Resource 2). All archived samples Results and discussion analyzed in this study were stored at a maximum temperature of −20 °C prior to shipment in coolers with dry ice via Surface sediment overnight courier to participating analytical labs. Ranging in concentration between 20 and 1,000 ng/g dry, the Target analytes most abundant target CECs in surface sediment were 4-NP and its mono- and di-ethoxylates (NP1EO and NP2EO) Measured analytes in both sediment and Mytilus tissue were (Fig. 2). Concentrations of 4-NP were higher than the mono- selected PPCPs (including triclosan and triclocarban, TCS and and di-ethoxylated series at both SFSM and MDSJ, indicating TCC, respectively), alkylphenols (including 4-nonylphenol or a weathered signature where ethoxycarboxylates are formed 4-NP), perfluorinated compounds (e.g., perfluorooctanoic ac- under oxic conditions, and a shortening of the ethoxylate side id and perfluorooctane sulfonate, PFOA and PFOS, respec- chain (e.g., NP2EO to NP1EO to NP) is expected under tively) and pesticides. Polybrominated diphenyl ethers anoxic conditions (Ferguson and Brownawell 2003). These (PBDEs) and legacy contaminants were measured in the sed- abundance results were corroborated by concentrations deter- iment core only. A complete listing of all target analytes and mined in a sample representing the surface layer of sediment reporting limits (Online Resource 3), as well as information from the PVS3C core, where 4-NP, NP1EO, and NP2EO were and chemical structures of CECs of particular interest (Online also the highest in abundance (800 to 900 ng/g), followed by Resource 4), is included as supplementary information. TCC at ~100 ng/g and miconazole at ~10 ng/g (Online Resource 5,ESMFig.3). Perfluorinated compounds, includ- Sample processing and analysis ing PFOA, PFOS, and perfluorooctane sulfonamide (PFOSA), a precursor to the former compounds, exhibited The majority of target CECs including PPCPs were analyzed only trace abundance in sediments from both stations using LC-MS/MS or GC-MS/MS by Axys Analytical (<10 ng/g). (Sidney, BC, Canada), who have established protocols based It is interesting to note apparent differences in CEC con- on recently standardized methods, including EPA Methods centrations and profiles between the sediment samples from 1694 and 1698. Eight common-use pyrethroids and 16 San Francisco Bay (SFSM) and southern California (MDSJ). PBDE congeners were analyzed using previously published Permethrin, a type I (non-cyano containing) pyrethroid insec- methods (Lao et al. 2010;Dodderetal.2012). Briefly, sedi- ticide, and cypermethrin, a type II (cyano-containing) pyre- ment samples were freeze-dried, extracted with dichlorometh- throid, both used widely throughout California in residential ane using pressurized fluid extraction, and analyzed by gas and commercial urban applications (Ahn et al. 2005; Weston chromatography-mass spectrometry operating in either the and Lydy 2010) were the second most abundant CECs in the electron or negative chemical ionization, and selection ion MDSJ sediment (~20 ng/g each). The observed pyrethroid monitoring modes (GC-EI [or NCI]-MS-SIM). concentrations were similar to those reported previously for estuarine sediments from Ballona Creek, an intensely Quality assurance and quality control hydromodified urban watershed that conveys runoff, but no point discharges of WWTP effluent, to the Pacific Ocean (Lao Data was screened against three main QA/QC criteria: (1) the et al. 2010). Pyrethroids were not detected in the SFSM sample concentration was at least two times the blank sediment sample, suggesting that runoff (and not WWTP Environ Sci Pollut Res

Fig. 2 Surface sediment CEC concentrations at the southern California Metformin did not pass the sediment core QC, and thus, no results are (MDSJ) and San Francisco Bay (SFSM) locations. The Palos Verdes (PV) presented. Plotted concentrations were transformed as log10(x+1), where surface sediment is the top 4 cm of the core. 4-Nonylphenol (4-NP), its x is the concentration. The tick marks on the y axes were adjusted for this mono- and di-ethoxylated derivatives (NP1EO, NP2EO), pyrethroids, transformation and triclocarban were among the most abundant contaminants. effluent) remains a major contributor of these biocides to the coast. Similarly, the higher concentrations of 4-NP and its ethoxylates in the MDSJ sediment sample indicate that runoff, possibly emanating from local marina sources, is a major contributor (Lao et al. 2012). In contrast, previous studies reported concentrations of 4-NP as high as 3,200 ng/g in sediments near marine WWTP outfalls (Schlenk et al. 2005), suggesting that infrequent, episodic overflows of un- or lightly treated wastewater into the Ballona Creek estuary from a high- capacity WWTP <10 km south of MDSJ may also have contributed to sediment loading at this location. Lastly, concentrations and loading of copper-based and organic (Irgarol) vessel antifouling formulations were found to be elevated in the water column and sediments of large boat basins, including Marina del Rey (Sapozhnikova et al. 2007;Maruyaand Schiff 2009). However, the input of CECs such as the alkylphenols into such waterbodies remains unknown.

Mussel tissue

Differences in abundance and no. detections Like surface sediments, the most abundant target CECs were 4-NP and NP1EO, exhibiting concentrations up to 300 and 700 ng/g wet weight, respectively (Fig. 3). Due to failure to meet QA/QC acceptance criteria, tissue concentrations of NP2EO were not available for comparison. In contrast to surface sediments, however, NP1EO concentrations were similar or higher than 4-NP, suggesting a possible higher relative accumulation potential for the NP1EO series. The ratio of tissue to sediment Fig. 3 Nonylphenol (4-NP) and its mono-ethoxylated derivatives concentration, also known as the bioaccumulation factor (NP1EO) were the most abundant CECs found in soft tissue of mussels – (BAF), was close to unity for 4-NP, coinciding with results (Mytilus spp.) collected from coastal stations for the period 1995 2006. In contrast to 4-NP and NP1EO, the number of detections of PPCPs such as from a previous field study on marine sediments and ibuprofen, lomefloxacin, and warfarin was less frequent. SFSM San hornyhead turbot (Pleuronichthys verticalis), a flatfish that Francisco Bay; MDSJ Marina del Rey; SSSS San Simeon Environ Sci Pollut Res inhabits the bottom near marine outfalls in southern California chlorpyrifos), no clear differences between MDSJ and (Maruya et al. 2012). Little comparative data is available for SFSM tissue concentrations were apparent. It was abundantly nonylphenol monoethoxylate BAFs. clear, however, that the mussels collected from the central Although numerous published data exist for the occurrence coast at San Simeon (SSSS) had far fewer detections, and of 4-NP in aquatic biota, relatively few studies are available furthermore, when detectable, concentrations were lower in for comparison of NP1EO and NP2EO in bivalves. For ex- comparison to the other stations. This is to be expected since ample, a study on clams (Donax trunculus) from the western this station is equidistant (~350 km) from the major metropol- Mediterranean reported NP as the predominant alkylphenol, at itan areas of southern California and San Francisco Bay, and concentrations up to 147 ng/g wet weight, with lower levels the surrounding land use is decidedly less impacted by human for mussels (Mytilus galloprovincialis) (Bouzas et al. 2010). development (Maruya et al. 2013a). Several CECs were only In California, the average concentration for mussels (Mytilus detected in the tissue samples from the WWTP-influenced californianus) collected in Morro Bay, a small inlet on the station in San Francisco Bay (SFSM), including the PPCPs central coast, was 122±35 ng/g wet (n=3) (Diehl et al. 2012). warfarin, sulfamethazine, metformin, and hydrocodone. In Concentrations of 4-NP, NP1EO, and NP2EO from a larger, contrast, permethrin, lomefloxacin, and cocaine were detect- statewide pilot study on Mytilus spp. collected at 69 coastal able in tissue samples from MDSJ and not in tissue samples sites during 2009-2010 averaged 94, 18, and 5 ng/g wet from SFSM, suggesting some degree of specificity of occur- weight, respectively, assuming a moisture content of 80 % rence based on the proximity to and thus influence of WWTP (Dodder et al. 2013). In this latter study, the maximum con- vs. stormwater permitted discharges. Such information will centrations of 4-NP, NP1EO, and NP2EO, converted from dry help inform future CEC monitoring and assessment efforts, weight tissue basis using 80 % average moisture content, were e.g., those based on proximity to urban areas and discharge 600, 60, and 86 ng/g wet, respectively. Reports to date show source/type (Maruya et al. 2013b). little evidence of accumulation of 4-NP, NP1EO, or NP2EO in higher aquatic biota, including fish in freshwater systems Time series (Keith et al. 2001; Ramirez et al. 2009). Ibuprofen, the active ingredient in commonly used, over- Depth profiles of CECs in a sediment core Repeated sampling the-counter analgesics, was also among the highest abundant and analysis of hydrophobic organic compounds in segment- CECs with concentrations ranging between 200–800 ng/g. ed sediment cores collected over the past three decades has Interestingly, the number of detections was limited to three revealed a well-defined layering of DDT-related compounds, samples. Several other PPCPs including hydrocodone, discharged into the nearshore marine environment from a lomefloxacin, metformin, naproxen, and sulfamethazine were WWTP outfall off the Palos Verdes shelf. The peak input of also detectable in only a limited number of time series sam- DDTs, as represented by p,p′-DDE, at ~30 cm in the PVS3C ples. Permethrin, one of the more abundant target CECs in core corresponds to a period in the early 1970s prior to surface sediment, was detected in a single mussel tissue sam- enactment of the Clean Water Act and advent of environmen- ple (MDSJ), confirming its low potential for bioaccumulation tally protective discharge regulations (Online Resource 5, (Maruya et al. 2012). Among the several PFCs analyzed, only ESM Fig. 4). Likewise, the depth profile of other legacy PFOSA, a perfluorinated precursor of PFOS and PFOA, was organochlorines, e.g., the chlordane-related cyclodiene pesti- detected in mussel tissue. Other studies have reported low to cides whose usage was restricted shortly after DDT, was undetectable concentrations of PFOA and PFOS in bivalves similar to that observed for p,p′-DDE. The peak observed used for aquatic monitoring purposes (Nania et al. 2009; for p,p′-DDE thus served as the datum for estimating the time Fernández-Sanjuan et al. 2013). However, homogenized periods represented by the composited sediment segments freeze-dried tissue of Mytilus edulis (SRM2974a, NIST) ana- analyzed in the present study (Table S2). lyzed in an interlaboratory comparison exercise showed that The depth profile observed for miconazole shows an in- concentrations of PFOSA were highest (22±0.2 ng/g dry) crease in sediment concentrations starting at ~15-cm depth all among 16 PFC analytes, including PFOS (3.5±0.19 ng/g) the way to the surface of the PVS3C sediment core (Fig. 4a). and PFOA (<0.62 ng/g) (Reiner et al. 2012). Thus, it follows Although miconazole concentrations were 10 to 100 times that PFOSA deserves consideration as a key PFC for moni- lower than other CECs targeted, the increasing trend in sedi- toring in aquatic biota. ment concentration indicates that input of this chemical in- creased from ~1990 through 2007. Although data on its Differences among sites Tissue concentrations for Mytilus historical use is scarce, the core profile suggests that micona- collected at SFSM and MDSJ overlapped for 4-NP and zole represents an example of a recently “emerged” environ- PFOSA, whereas concentrations of NP1EO were higher for mental contaminant. SFSM compared to MDSJ (Fig. 3). For several lower abun- A slightly different picture was presented by the depth dance CECs (e.g., enrofloxacin, naproxen, diazinon, and profiles for BDE-47, -99, and -100, congeners that are Environ Sci Pollut Res

Thus, PBDEs are an example of a more recent, but already emerged (and now declining), environmental contaminant. In contrast to the examples provided above but similar to the legacy organochlorines discussed previously, the depth profile for TCC shows a broadened peak centered at 30-cm depth, corresponding to the early 1970s (Fig. 4c). On the other hand, the depth profile for TCS shows a rapid increase begin- ning at roughly the same depth (and thus time period) as the peak for p,p′-DDE and TCC, followed by a slower, but still increasing, trend in more recently deposited sediment. Moreover, the concentration of TCC is several-fold higher than for TCS in all composited core segments. Miller et al. (2008) also reported several-fold higher concentrations of TCC compared to TCS, peaking at roughly the same time period (1970–1980s), in a sediment core from Jamaica Bay (NY, USA). In another study, the mass loading of TCC and TCS from wastewater treatment plants in the urban environment (Baltimore, MD, USA) as well as their sediment half- lives were reported to be similar (Halden and Paull 2005). The results for TCC in the present study are consistent with Miller et al. (2008) and suggest that usage and subsequent input of TCC have declined since its peak in the 1970–1980s. This is not the case for TCS, which exhibited an increasing trend in concentration until the time of core collection (i.e., 2007), suggesting continued increase in usage and input of this antimicrobial agent into coastal receiving waters. The depth profile for 4-NP was similar to the legacy organochlorines and TCC that peaked at ~30 cm (ca. 1970) followed byasteadydeclinetotimeofcorecollection(Fig.S4).No discernable down core trend was apparent for NP1EO and NP2EO, whose concentrations hovered below 500 ng/g throughout the time period represented by this core (~1950– 2007). Moreover, the concentrations of 4-NP were several-fold Fig. 4 Concentration depth profiles of a miconazole; b polybrominated greater than for its mono- and di-ethoxylated homologs diphenyl ether (PBDE) congeners; c triclocarban and triclosan in a throughout most core depths, peaking at 2,500 ng/g and con- sediment core collected in 2007 from a marine Superfund site off the coast of California (USA). The inset in c shows the increase in triclosan verging to a concentration similar to the ethoxylates at the core concentration. Duplicate samples were analyzed for the core slice with a surface. Isobe et al. (2001) also reported a subsurface concen- midpoint at 23 cm. Time periods were estimated from the peak input of tration maximum for alkylphenols (including NP) correspond- DDT from a nearby marine outfall (ca. 1970) ing to sediment layers deposited in the mid-1970s in cores collected from Tokyo Bay, Japan, which they attributed to the common environmental contaminants in aquatic and terrestri- effect of regulations for industrial wastewater in the early al systems. Invariably, these profiles exhibited a concurrent 1970s. In contrast, Ferguson et al. (2003) found total NPEO peak in sediment concentration at ~10-cm depth, correspond- concentrations to decrease with increasing depth for sediment ing to a time frame in the mid-1990s, followed by a consistent cores collected near a WWTP outfall in Jamaica Bay, NY decreasing trend in concentration to the surface of the PVS3C (USA), suggesting increasing usage up through the end of the core (Fig. 4b). This temporal profile corresponds to other twentieth century. Although we cannot offer a simple, satisfac- studies using dated cores from a south China estuary and the tory explanation for the observed declining vs. static profiles U.S. Great Lakes region (Chen et al. 2007; Bradley et al. for 4-NP, NP1EO, and NP2EO, what remains clear is that the 2011). The temporal trend observed in the present study is input and occurrence of alkylphenols is not a recent also consistent with reported trends in biota representing phenomenon. different trophic levels, e.g., bivalves, fish, and marine mam- mals for the period from the 1970s to the present (Law et al. Mussel tissue (1995–2007) The time series concentrations of 2006; Environmental Canada 2012; Kajiwara et al. 2004). 4-NP and NP1EO in Mytilus tissue show a clear declining Environ Sci Pollut Res trend for both the San Francisco Bay (SFSM) and southern that PPCPs such as ibuprofen, lomefloxacin, miconazole, and California (MDSJ) stations (Fig. 5). This trend follows the sulfamethazine and PFCs (e.g., PFOS, PFOA, PFOSA) were decreasing trend noted for 4-NP in the PVS3C sediment core detectable. The most abundant contaminants, however, were and indicates that mussels are a relevant (i.e., quick- still 4-NP, NP1EO and NP2EO, TCC, and (at the stormwater responding) biosentinel of exposure to chemicals associated impacted station only) the pyrethroid insecticides permethrin with surface sediments. Tissue concentrations for Mytilus and cypermethrin. Of these, the alkylphenols, ibuprofen, and collected from the relatively undeveloped area near San PFOSA occurred in the greatest abundance in mussel tissue. Simeon (SSSS) did not appear to increase or decrease over the time period. One concern when utilizing long-term ar- What trends in CEC occurrence and input can we expect in the chives for scientific research is the integrity and cross- future? The historical record in a well-preserved sediment contamination of preserved samples. The low background core collected near the marine outfall of a large WWTP concentrations of 4-NP and NP1EO associated with the revealed (1) increasing concentrations of selected CECs SSSS tissue samples, coupled with the apparent absence of (e.g., miconazole, TCS) toward the core surface; (2) peak any decreasing time trend, indicates that sample integrity was concentrations of 4-NP and TCC corresponding to the not compromised or degraded over time, at least for this 1970s; and (3) a recent peak in concentration for PBDE category of targeted CECs. Alkylphenols were the only CEC congeners (corresponding to the mid-1990s). Core data indi- analytes for which detections at multiple time points allowed cate declines in 4-NP, TCC, and PBDEs, but not for NP1EO for determination of a temporal trend. and NP2EO (or as noted TCS). Thus, we can anticipate stable or increasing occurrence and potential for environmental exposure in future years for those CECs whose production and Summary and conclusions usage will continue at current levels or increase (e.g., certain PPCPs). Conversely, we would expect CECs whose produc- What “CECs” were actually present several decades tion has or soon will be reduced and/or eliminated altogether ago? Analysis of archived sediment core samples from (e.g., PBDEs) to continue declining. It is also important to California coastal and marine ecosystems revealed that 4- note that replacement chemicals (e.g., chlorinated phosphate NP, NP1EO, and NP2EO, as well the antimicrobials TCC flame retardants such as TCEP, TCPP, and TDCPP) may not and TCS, were abundant in sediment deposited in the 1970s. persist or bioaccumulate to the extent of its predecessors (e.g., These contaminants were also detected in coastal bivalve PBDEs); however, they may be relevant for future monitoring tissue (Mytilus spp.) collected from the California coast during in other media, such as the aqueous phase in receiving water the mid-1990s. A number of PPCPs (e.g., ibuprofen, micon- systems (Alvarez et al. 2013). azole) and current-use pesticides (e.g., pyrethroids) were not These data could be used to support three levels or “tiers” detected in these archived samples. of current/future monitoring and assessment activities (Maruya et al. 2013). Tier 1 (“highest concern”) would consist What CECs were present most recently (2007–2009)? Analysis of frequent (annual) monitoring of CECs that show an increas- of surface sediments and Mytilus collected in 2007 showed ing trend or whose concentrations exceed risk-based monitoring thresholds. Triclosan, PFCs, and perhaps PPCPs such as ibuprofen and miconazole would be possible examples of tier 1 CECs. The second tier (moderate concern) would employ periodic (every 3 to 5 years) monitoring to ensure concentrations continue to decline or stay below thresholds of concern (e.g., PBDEs). Tier 3 (“low” concern) would employ infrequent (every 10 years or less) or no monitoring effort and would include those CECs that are un- or barely detectable, but whose usage may continue or increase in the future. This last category could also apply to legacy POPs (e.g., DDTs, PCBs), whose concentrations, spatial, and temporal trends have been well-established. The information gleaned from such monitoring should be directed toward addressing questions deemed to be of importance by the scientific and management communities. However, it should be noted that the Fig. 5 Concentration of nonylphenol (4-NP) and nonylphenol mono- present study was limited in geographical scope to the highly ethoxylates (NP1EO) in mussel tissue (Mytilus spp.) for the time period 1995–2009. SFSM San Francisco Bay; MDSJ Marina del Rey; SSSS San urbanized southern California coast. As a result, CECs de- Simeon scribed herein should be viewed as illustrative examples for Environ Sci Pollut Res prioritized monitoring; the input history and temporal catalog Ferguson PL, Bopp RF, Chillrud SN, Aller RC, Brownawell BJ (2003) of these and other CECs may differ across regions and coast- Biogeochemistry of nonylphenol ethoxylates in urban estuarine sediments. Environ Sci Technol 37:3499–3506 lines worldwide. 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