Occurrence of contaminants of emerging concern along the California coast (2009–10) using passive sampling devices David A. Alvarez a,⇑ , Keith A. Maruya b , Nathan G. Dodder b , Wenjian Lao b , Edward T. Furlong c , Kelly L. Smalling d a U.S. Geological Survey, 4200 New Haven Road, Columbia, MO 65201, United States b Southern California Coastal Water Research Project, 3535 Harbor Boulevard, Suite 110, Costa Mesa, CA 92626, United States c U.S. Geological Survey, National Water Quality Laboratory, Denver Federal Center, Denver, CO 80225, United States d U.S. Geological Survey, 6000 J Street, Placer Hall, Sacramento, CA 95819, United States article info Keywords: POCIS SPME PED Emerging contaminants Mussels abstract Three passive sampling devices (PSDs), polar organic chemical integrative samplers (POCIS), polyethylene devices (PEDs), and solid-phase microextraction (SPME) samplers were used to sample a diverse set of chemicals in the coastal waters of San Francisco Bay and the Southern California Bight. Seventy one chemicals (including fragrances, phosphate flame retardants, pharmaceuticals, PAHs, PCBs, PBDEs, and pesticides) were measured in at least 50% of the sites. The chemical profile from the San Francisco Bay sites was distinct from profiles from the sites in the Southern California Bight. This distinction was not due to a single compound or class, but by the relative abundances/concentrations of the chemicals. Com- paring the PSDs to mussel (Mytilus spp.) tissues, a positive correlation exists for the 25 and 26 chemicals in common for the PEDs and SPME, respectively. Diphenhydramine was the only common chemical out of 40 analyzed in both POCIS and tissues detected at a common site. Published by Elsevier Ltd. 1. Introduction The National Oceanic and Atmospheric Administration’s National Status and Trends Mussel Watch Program has analyzed bivalves since 1986 to characterize spatial and temporal trends of contaminants in the coastal areas of the United States. Bivalves can be a useful sentinel species for contaminant monitoring pro- grams as they remain in fixed locations and are good accumulators of persistent, bioaccumulative, and toxic (PBT) organics. This long- term monitoring program has shown that levels of the banned or restricted chlorinated organics such as polychlorinated biphenyls (PCBs) and organochlorine pesticides have decreased compared to historical values (Kimbrough et al., 2008). With the levels of many PBTs decreasing, the research focus is beginning to shift to ‘‘contaminants of emerging concern’’ (or CECs). CECs is a term encompassing a broad range of chemicals not traditionally part of monitoring studies such as pharmaceuti- cals, fragrances, flame retardants, and current-use pesticides. These CECs sometimes lack the persistence of traditional chlorinated organics, but due to their continual input into the environment from industrial, agricultural, and urban sources, they maintain a pseudo-persistence (Daughton and Ternes, 1999). Long-term exposure to some CECs has been shown to cause sub-lethal effects such as endocrine disruption in aquatic species including mussels (Gagné et al., 2004; Porte et al., 2006; Matthiessen, 2008). The measurement of PBTs and CECs in open waters can be difficult using traditional grab sampling techniques as the concen- trations of these chemicals are often at levels below the method detection limits achievable with a standard 1 l water sample (Alvarez and Jones-Lepp, 2011). The use of passive sampling techniques can overcome the volume limitations of grab samples and be used to sample CECs which do not bioaccumulate in typical biomonitoring organisms. In this work, three types of passive sampling devices (PSDs), the polar organic chemical integrative sampler (POCIS), low density polyethylene film devices (PEDs), and solid phase microextraction (SPME) fibers were co-deployed in arrays to measure concentrations of PBTs and CECs along the California coast. 2. Materials and methods 2.1. Sampling locations The PSD arrays were deployed at 11 stations for periods of 28– 30 days along the California’s San Francisco Bay and the Southern California Bight (Table 1 and Fig. 1). These stations comprised a mixture of land-use from highly urban (number of sites, 6), mixed 0025-326X/$ - see front matter Published by Elsevier Ltd. http://dx.doi.org/10.1016/j.marpolbul.2013.04.022 ⇑ Corresponding author. Tel.: +1 573 441 2970. E-mail address: [email protected](D.A. Alvarez). Marine Pollution Bulletin xxx (2013) xxx–xxx Contents lists available at SciVerse ScienceDirect Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul Please cite this article in press as: Alvarez, D.A., et al. Occurrence of contaminants of emerging concern along the California coast (2009–10) using passive sampling devices. Mar. Pollut. Bull. (2013), http://dx.doi.org/10.1016/j.marpolbul.2013.04.022
Transcript
Marine Pollution Bulletin xxx (2013) xxx–xxx
Contents lists available at SciVerse ScienceDirect
Occurrence of contaminants of emerging concern along the California coast(2009–10) using passive sampling devices
David A. Alvarez a,⇑, Keith A. Maruya b, Nathan G. Dodder b, Wenjian Lao b, Edward T. Furlong c,Kelly L. Smalling d
a U.S. Geological Survey, 4200 New Haven Road, Columbia, MO 65201, United Statesb Southern California Coastal Water Research Project, 3535 Harbor Boulevard, Suite 110, Costa Mesa, CA 92626, United Statesc U.S. Geological Survey, National Water Quality Laboratory, Denver Federal Center, Denver, CO 80225, United Statesd U.S. Geological Survey, 6000 J Street, Placer Hall, Sacramento, CA 95819, United States
a r t i c l e i n f o
Keywords:POCISSPMEPEDEmerging contaminantsMussels
0025-326X/$ - see front matter Published by Elsevierhttp://dx.doi.org/10.1016/j.marpolbul.2013.04.022
Please cite this article in press as: Alvarez, D.A.,sampling devices. Mar. Pollut. Bull. (2013), http
a b s t r a c t
Three passive sampling devices (PSDs), polar organic chemical integrative samplers (POCIS), polyethylenedevices (PEDs), and solid-phase microextraction (SPME) samplers were used to sample a diverse set ofchemicals in the coastal waters of San Francisco Bay and the Southern California Bight. Seventy onechemicals (including fragrances, phosphate flame retardants, pharmaceuticals, PAHs, PCBs, PBDEs, andpesticides) were measured in at least 50% of the sites. The chemical profile from the San Francisco Baysites was distinct from profiles from the sites in the Southern California Bight. This distinction was notdue to a single compound or class, but by the relative abundances/concentrations of the chemicals. Com-paring the PSDs to mussel (Mytilus spp.) tissues, a positive correlation exists for the 25 and 26 chemicalsin common for the PEDs and SPME, respectively. Diphenhydramine was the only common chemical out of40 analyzed in both POCIS and tissues detected at a common site.
Published by Elsevier Ltd.
1. Introduction
The National Oceanic and Atmospheric Administration’sNational Status and Trends Mussel Watch Program has analyzedbivalves since 1986 to characterize spatial and temporal trendsof contaminants in the coastal areas of the United States. Bivalvescan be a useful sentinel species for contaminant monitoring pro-grams as they remain in fixed locations and are good accumulatorsof persistent, bioaccumulative, and toxic (PBT) organics. This long-term monitoring program has shown that levels of the banned orrestricted chlorinated organics such as polychlorinated biphenyls(PCBs) and organochlorine pesticides have decreased comparedto historical values (Kimbrough et al., 2008).
With the levels of many PBTs decreasing, the research focus isbeginning to shift to ‘‘contaminants of emerging concern’’ (orCECs). CECs is a term encompassing a broad range of chemicalsnot traditionally part of monitoring studies such as pharmaceuti-cals, fragrances, flame retardants, and current-use pesticides. TheseCECs sometimes lack the persistence of traditional chlorinatedorganics, but due to their continual input into the environmentfrom industrial, agricultural, and urban sources, they maintain apseudo-persistence (Daughton and Ternes, 1999). Long-term
Ltd.
et al. Occurrence of contaminan://dx.doi.org/10.1016/j.marpolb
exposure to some CECs has been shown to cause sub-lethal effectssuch as endocrine disruption in aquatic species including mussels(Gagné et al., 2004; Porte et al., 2006; Matthiessen, 2008).
The measurement of PBTs and CECs in open waters can bedifficult using traditional grab sampling techniques as the concen-trations of these chemicals are often at levels below the methoddetection limits achievable with a standard 1 l water sample(Alvarez and Jones-Lepp, 2011). The use of passive samplingtechniques can overcome the volume limitations of grab samplesand be used to sample CECs which do not bioaccumulate in typicalbiomonitoring organisms. In this work, three types of passivesampling devices (PSDs), the polar organic chemical integrativesampler (POCIS), low density polyethylene film devices (PEDs),and solid phase microextraction (SPME) fibers were co-deployedin arrays to measure concentrations of PBTs and CECs along theCalifornia coast.
2. Materials and methods
2.1. Sampling locations
The PSD arrays were deployed at 11 stations for periods of 28–30 days along the California’s San Francisco Bay and the SouthernCalifornia Bight (Table 1 and Fig. 1). These stations comprised amixture of land-use from highly urban (number of sites, 6), mixed
ts of emerging concern along the California coast (2009–10) using passiveul.2013.04.022
Table 1Passive sampler deployment stations for the California pilot study on contaminants of emerging concern (CECs) in 2009–10 (arranged north to south).
Station name Latitude/longitude Land-use category Mussel sampling location (lat/long)a
SPPR/San Pablo Bay – Petaluma River 38.13378/�122.501 Low development NoneSFYB/San Francisco-Yerba Buena 37.81375/�122.359 Urban Nearby
37.8152/�122.371SPNR/San Pablo Bay – Napa River 38.29931/�122.283 Ag NoneSFSB/San Francisco Bay – South Bay 37.46053/�121.975 Urban NoneCPSB/Carpenteria State Beach 34.38693/�119.514 Low development Nearby
34.38712/�119.514MULG/Mugu Lagoon 34.10212/�119.104 Ag Nearby
34.1023/�119.104LATI/Los Angeles Harbor Terminal Island 33.722/�118.243 Urban Co-deployedLARM/LA River-Queen Mary 33.75523/�118.195 Urban Nearby
33.75525/�118.195NHPB/Newport Harbor PCH Bridge 33.61695/�117.904 Mixed development Nearby
33.6166/�117.905SDHI/San Diego-Harbor Island 32.7248/�117.195 Urban Nearby
32.72478/�117.195TJRE/Tijuana River Estuary 32.56988/�117.127 Urban Nearby
32.56982/�117.127
a Dodder et al. (this issue).
Fig. 1. Passive sampler deployment locations during the 2009–10 pilot study on contaminants of emerging concern (CECs) along the California coast in San Francisco Bay andthe Southern Bight.
Please cite this article in press as: Alvarez, D.A., et al. Occurrence of contaminants of emerging concern along the California coast (2009–10) using passivesampling devices. Mar. Pollut. Bull. (2013), http://dx.doi.org/10.1016/j.marpolbul.2013.04.022
development (1), low development (2) to largely agricultural (2).Four of the stations received permitted stormwater discharges,one received discharge from a publicly owned treatment works(POTWs) only, three received discharges from both stormwaterand POTWs, and three were not within proximity to regulated dis-charges. Details on how the land-use categories were determinedand discharge identification are given by Maruya et al. (this issue).
2.2. Passive sampling devices
At each station, POCIS, PEDs, and SPME fibers were deployedsubtidally within 500 m of a corresponding mussel sampling loca-tion. At four of the PSD stations (LATI; SFSB; SPNR; and SPPR), nonative mussels were available for collection therefore caged mus-sels (Mytilus spp.) were co-deployed with the PSDs. A complete listof the chemicals analyzed from each PSD (166 in POCIS, 95 in PEDs,and 99 in SPME) is given in Table SI-1.
2.2.1. POCISFor each deployment site, a stainless steel deployment canister
housing five POCIS (41 cm2 sampling surface area, 200 mg of OasisHLB each) was prepared according to established procedures (Alva-rez et al., 2004). The loaded deployment canisters were shipped tothe study sites on ice in airtight metal cans. At the deploymentsites, they were quickly attached to the PSD arrays with nylonropes and metal clips and secured in the water. Upon retrieval,the canisters were placed back in the metal cans and shipped tothe laboratory in coolers on ice for processing.
ness, 1.2 g each, Covalence, Minneapolis, MN, USA) were pre-cleaned by sonication (3 � 15 min) using methylene chloride, fol-lowed by methanol, and then deionized water. The pre-cleanedstrips were threaded onto solvent rinsed copper wire, wrapped inaluminum foil and stored at �20 �C or ice until deployment. Trip-licate PEDs were attached onto polypropylene rope with stainlesssteel hose clamps for deployment at each site. Upon retrieval, eachPED was gently wiped with a Kimwipe to remove visible residueand rinsed with deionized (DI) water. The PEDs were placed inindividual precleaned glass vials and transported on ice to thelaboratory.
2.2.3. SPMENew SPME fibers coated with 100 lm polydimethylsiloxane
(Supelco Inc., Bellefonte, PA, USA) were pre-conditioned by heatingat 250 �C for 0.5 h prior to insertion into a perforated copper casingto protect against breakage and biofouling (Zeng et al., 2004; Fer-nandez et al., 2012). The SPME fibers were attached in triplicateto the PEDs at each site using metal clips and nylon rope. Followingthe field deployment, the SPME fibers were placed in glass vialsand transported on ice to the laboratory.
2.3. Analytical methods
2.3.1. POCISThe POCIS were removed from the deployment canisters and
rinsed with DI water to remove any particles that may fall intothe extraction cartridges. Each POCIS was carefully opened andthe sorbent transferred with DI water into pre-cleaned empty so-lid-phase extraction (SPE) cartridges (25 mL, Biotage, Charlotte,NC). The sorbent was dried by pulling (by vacuum) air throughthe sorbent bed for 10 min. Once dry, the sorbents were designatedfor analysis of waste indicator compounds (2 POCIS per site), phar-maceuticals (2 POCIS per site), and pesticides (1 POCIS per site).
Please cite this article in press as: Alvarez, D.A., et al. Occurrence of contaminansampling devices. Mar. Pollut. Bull. (2013), http://dx.doi.org/10.1016/j.marpolb
The two POCIS for the waste indicator compounds were eachextracted with 25 mL of 80:20 (v:v) dichloromethane:methyl-tert-butyl (Optima grade, Fisher Scientific) ether prior to beingcombined into a single sample and reduced in volume to 2–3 mLby rotary evaporation. The concentrated extracts were dried bypassing them through filter cartridges (Captiva 3 mL, Agilent Tech-nologies) containing a layer of anhydrous sodium sulfate. The driedextracts were reduced in volume under nitrogen, transferred intogas chromatography (GC) vials, spiked with 500 lg of p-ter-phenyl-d14 as an instrumental internal standard and adjusted toa final volume of 1 mL. Analyses were performed using an Agilent6890 GC coupled to a 5973 N quadrupole mass selective detector(MSD) operated in full scan positive ion electron ionization (EI)mode. Details on the instrument conditions have been previouslyreported (Alvarez et al., 2009).
The two POCIS for the pharmaceuticals were each extracted with25 mL of methanol (Optima grade, Fisher Scientific), which was sub-sequently evaporated to 2–3 mL by rotary evaporation prior to beingcombined into a single sample. The samples were concentrated to<1 mL under nitrogen and solvent exchanged into water for analysisby high-performance liquid chromatography/tandem mass spec-trometry (HPLC/MS/MS). Details of the method are described inTertuliani et al. (2008). The HPLC/MS/MS analyses used an ammo-nium formate-modified water:methanol gradient to separate thepharmaceuticals on a reversed-phase C-18 stationary phase column.Electrospray ionization operated in the positive-ion mode was usedfor identification and quantification of the target pharmaceuticals.For each pharmaceutical, a protonated pseudomolecular precursorion was formed during ionization and subsequently fragmented inthe MS/MS. At least two characteristic product fragment ions formedfrom the precursor ion were monitored for each pharmaceutical.Qualitative identification of each pharmaceutical was based on theHPLC retention times and relative abundances of these diagnosticprecursor-product transitions, and quantitation of the more abun-dant primary transition was used to determine individual pharma-ceutical concentrations in the extracts. Quantitation was by theinternal standard method using ethyl nicotinoate-d4, carbamaze-pine-d10, fluoxetine-d5, and norfluoxetine-d5 which were added tothe extracts prior to analysis.
The remaining POCIS for current-use pesticides was also ex-tracted with 25 mL of methanol and evaporated by rotary evapora-tion. Atrazine-d10 was added as a recovery surrogate. The extractswere exchanged into ethyl acetate, reduced to a final volume of0.5 mL, and acenaphthene-d10 and pyrene-d10 were added as inter-nal standards. Analyses were performed using an Agilent 7890 GCcoupled to a 5975 MSD operating in EI mode. Details on the instru-ment conditions have been previously reported (Reilly et al., 2012).
2.3.2. PEDs and SPMEThe PEDs were cut into small pieces, placed in solvent rinsed glass
bottles, spiked with dibromooctafluorobiphenyl (DBOFB) and PCB208 (as recovery surrogates), and sonicated for 15 min with3 � 300 mL of dichloromethane. The combined dichloromethaneextract was dried over anhydrous sodium sulfate and concentratedto about 5 mL and then exchanged to hexane to a final volume of0.5 mL using a TurboVap II Concentration Workstation (Caliper LifeSciences, Hopkinton, MA, USA). The extract was transferred to a GCvial and spiked with PCBs 30 and 205 as internal standards.
Polybrominated diphenyl ethers (PBDEs), PCB congeners with 5or more chlorine atoms, pyrethroids, and fipronil and its threedegradates (Table SI-1) were analyzed using an Agilent 7890 GCcoupled to a 5975C quadrupole MSD (Wilmington, DE, USA) oper-ating in the negative chemical ionization (NCI) mode. Polycyclicaromatic hydrocarbons (PAH) and PCB congeners with less than5 chlorine atoms (18, 28, 37, 44, 49, and 52) were analyzed on asimilar instrument operating in the EI mode (70 eV). Details for
ts of emerging concern along the California coast (2009–10) using passiveul.2013.04.022
Table 2Mean, minimum and maximum concentrations of contaminants of emerging concern (CECs) and legacy analytes detected in passive sampling devices at 50% or more of the studysites.
these analyses were published previously (Fernandez et al., 2012).A single quantitation ion per target compound was acquired usingthe selected ion monitoring (SIM) mode. SPME fibers were manu-ally injected into the GC inlet; two fibers were analyzed in theNCI mode and a single fiber was analyzed in the EI mode. For thestations with duplicate SPME, one each was analyzed in the NCIand EI modes. Five-point external (SPME) and internal (PED) stan-dard calibration curves were used to quantify target compounds.Analyte-specific method detection limits (MDLs) were estimatedusing the lowest detectable target analyte mass for a minimum sig-nal to noise ratio of 3.
2.4. Quality assurance/quality control (QA/QC)
A QA/QC approach using a comprehensive set of performance-based data quality control objectives was used in this study
Please cite this article in press as: Alvarez, D.A., et al. Occurrence of contaminansampling devices. Mar. Pollut. Bull. (2013), http://dx.doi.org/10.1016/j.marpolb
(Maruya et al., this issue). This included field blanks, surrogate recov-ery checks, replicate samples, and data validation checks (Alvarezet al., 2007). The results from replicate PSDs deployed at MUGU andYBI were averaged. Final concentrations were blank subtracted.
2.4.1. POCISTetrachloroethylene (37%) and triethyl phosphate (167%) were
removed from the data set due to their low or high recovery inthe spiked matrix. Cholesterol was removed from the data setdue to a high duplicate sample relative percent difference (RPD)of 124%. The results for the three POCIS compound classes (waste-water compounds, pharmaceuticals, and pesticides) met theproject’s acceptance criteria. The recovery of the matrix spikesfor all detected wastewater compounds in the data set ranged from65% to 150%. In the set of duplicate deployments, all compoundssignificantly above the detection limit had RPDs 654%, except for
ts of emerging concern along the California coast (2009–10) using passiveul.2013.04.022
Fig. 2. Heat map showing hierarchical clustering of stations and analytes. The abundance key is shown on the left, with the abundance for calibrated POCIS analytescorresponding to ng/L and for calibrated SPME/PED analytes corresponding to pg/L. For non-calibrated analytes the abundance corresponds to ng/sampler matrix for POCISand pg/sampler matrix for SPME/PED.
diethylhexylphthalate (DEHP) at 156%. For pharmaceuticals, thesolvent exchange/blowdown recovery was �25% to 32%, wherenegative values represent a loss of compound, and positive valuesrepresent an apparent gain of compound. In the set of duplicatedeployments, all compounds significantly above the detection lim-it had RPDs 660%. For the pesticides, surrogate (atrazine-d10)recoveries were between 85% and 121%. In the set of duplicatedeployments, all compounds significantly above the detection lim-it had RPDs 642%.
2.4.2. PEDs and SPMEAll analytes from the PEDs and SPME analyses passed the accep-
tance criteria and were included in the data set. Recovery(mean ± sd) of surrogates in PED extracts was 79 ± 15 and96 ± 5.7 for DBOFB and PCB 208, respectively. Estimated concentra-tions for analytes that were detectable on SPME travel blanks were<10% of the reported MDLs, except for chlordane and p,p0-DDD(both 12%). Estimated concentrations for analytes detectable inPED procedural and travel blanks were in some cases comparableto the reported MDL (e.g. heptachlor epoxide, o,p0DDT, PCB 153/168) but were <10% of reported sample concentrations.
3. Results and discussion
3.1. Chemical profiles compared to land use
The PSDs were deployed at eleven sites along the Southern Cal-ifornia Bight (SCB) and San Francisco Bay (SF Bay). Seventy-oneindividual chemicals were measured by the PSDs in at least 50%of the sites (Table 2). The POCIS detected 17 compounds (fra-grances, phosphate flame retardants, plasticizers, and pharmaceu-ticals) while the SPME and PEDs detected 29 and 44 compounds(PAHs, PCBs, PBDEs, and chlorinated pesticides), respectively. Dueto the widespread urbanization along the California coast, onlysix current-use agricultural pesticides were detected at two sites(MULG/Mugu Lagoon and NHPB/Newport Harbor).
Please cite this article in press as: Alvarez, D.A., et al. Occurrence of contaminansampling devices. Mar. Pollut. Bull. (2013), http://dx.doi.org/10.1016/j.marpolb
Fig. 2 is a heat map showing the concentration of each analyteat each station as a color. The x- and y-axes were ordered by hier-archical clustering, resulting in the placement of stations and ana-lytes with similar patterns near one another. Dendrogramsshowing the relationship information are positioned on the sidesof the grid. The heat map was generated with POCIS analytes;PAH analytes from SPME; and PCB, OC, and PBDE analytes fromPEDs. This combination was selected because the PAH analyte setwas larger for SPME than PED, and PED was more sensitive towardsPCBs, OCs, and PBDEs than SPME. All analytes detected in at leastone sample were included. The abundances for POCIS and SPME/PED are in different units in order to visualize the contaminantprofiles on the heat map (see figure caption). Stations LARM andLATI are absent due to incomplete data sets.
The heat map shows the SF Bay contaminant profile is distinctfrom the SCB profile (that is, the four SF Bay stations are clusteredat the top of the heat map; the 5 SCB stations are clustered at thebottom). Stations are not clustered by land use, perhaps due to thelow statistical power resulting from the limited number of stationswithin each land use category. The distinction between SF Bay andthe SCB is tentative due to the small number of stations. The appar-ent distinction is not due to a single compound class; for example,the analytes making up cluster 1 (highlighted in Fig. 2) and foundat higher relative abundance in SF Bay are indole, PCB-52, PCB-101,PCB-138, DEET, heptachlor epoxide B, and endrin. The analytesmaking up cluster 2 and found at relatively high abundance atP8 stations from both SF Bay and the SCB are phenanthrene, fluo-ranthene, pyrene, diphenyl phthalate, and tris(1-chloro-2-pro-pyl)phosphate (TCPP). An expanded version of the heat mapnaming all analytes is provided in the Supporting information(Fig. SI-1).
3.2. Comparison of POCIS/PEDs/SPME
Comparisons between the hydrophilic POCIS (focusing on cur-rent-use and emerging contaminants) and the hydrophobic PED
ts of emerging concern along the California coast (2009–10) using passiveul.2013.04.022
Fig. 3. Comparison of mussel (Mytilus spp.) tissue concentrations of persistent, bioaccumulative and toxic (PBT) organics (Dodder et al., this issue) and ambient waterconcentrations estimated from SPME and PED measurements. The solid line is the best-fit regression, the dashed lines are the confidence band, and dotted lines are theprediction band.
and SPME (both mainly focusing on legacy contaminants) werelimited as each PSD was analyzed for different suites of chemicalswhich were likely to be sampled by that device. However, therewas some overlap between PSDs as many of the analytical methodscontained chemicals with a broad range of polarities. None of the15 chemicals in common between the POCIS and SPME or the ninechemicals in common between the POCIS and PED were detectedin both samplers. Nearly all of the common chemicals, with theexception of diazinon (not detected by any sampler) and the fipro-nil degradation products, have logKows greater than 4 and there-fore have a much lower affinity for the POCIS.
There were 71 common chemicals measured in both the PEDand SPME. Overall, there was good agreement between these twosamplers in terms of chemicals detected and estimated water con-centrations (Tables SI-2, SI-3, SI-4). The PED did have a highernumber of detections, all of which were at a lower estimated waterconcentration compared to the SPME, suggesting the PED may bemore useful in trace level applications.
The amount of chemical sampled is related to the volume of thereceiving phase in the PSD. In this study, the volume of the PDMSsorptive layer coated on the SPME fiber was approximately0.612 lL compared to a PED volume of 1300 lL. At equilibrium,the freely dissolved aqueous phase concentration (Cw) for a hydro-phobic chemical sampled by both devices is represented using theequation:
Cw ¼NPSD
KPSDVPSDð1Þ
where NPSD is mass of the chemical taken up by the receiving phase;KPSD is the PSD-water partition coefficient, and VPSD is the volume of
Please cite this article in press as: Alvarez, D.A., et al. Occurrence of contaminansampling devices. Mar. Pollut. Bull. (2013), http://dx.doi.org/10.1016/j.marpolb
the receiving phase. Using PCB congener 52 as an example, the PEDwas able to detect much lower concentrations of chemicals in thewater even though its KPSD was somewhat less compared to SPME(250,000 vs. 330,000) (Booij et al., 2003; Zeng et al., 2004). This isdue to the much larger sorptive volume of PEDs compared to theSPME fibers used in the present study. It follows that PEDs maybe more useful when targeting ultra-trace level (i.e. pg/L range)concentrations. However, the application of PEDs comes at a costof additional post-sampling processing effort that is eliminatedwhen utilizing SPME. Thus, practitioners are encouraged to care-fully consider the measurement objectives when targeting PBT con-taminants prior to selecting the appropriate PSD.
The POCIS hold a unique position among the PSDs used in thisstudy. The use of a polyfunctional sorbent matrix, such as the OasisHLB used in the POCIS in this study, provides different means ofretaining more polar chemicals (Alvarez et al., 2007) than the basicpartitioning of hydrophobic chemicals into SPME or PED. Thismeans the POCIS is better considered as a complementary passivesampling technique to SPME and PEDs, rather than evaluating it di-rectly via a common set of analyses.
3.3. Comparison of PSDs to tissue
A series of hydrophobic chemicals including PAHs, PCBs, andchlorinated pesticides covering a range of logKows from 4.1 to 8.1were found to bioaccumulate in mussel tissues and also sampledby the SPME and PED (Dodder et al., this issue). Twenty-six com-pounds were measured in both the SPME and tissues including12 PAHs, 10 PCB congeners, and four chlorinated pesticides. ThePED and tissues had 25 compounds in common with three PAHs,
ts of emerging concern along the California coast (2009–10) using passiveul.2013.04.022
Fig. 4. Comparison of mussel (Mytilus spp.) tissue concentrations of contaminants of emerging concern (CECs) (Dodder et al., this issue) and ambient water concentrationsestimated from POCIS measurements.
16 PCB congeners, and six chlorinated pesticides. Water concentra-tions estimated by the PSDs were positively correlated (p < 0.05)with mussel tissue concentrations for PAHs (both SPME andPED); for PCBs by PED; and for OC pesticides by SPME (Fig. 3).The Pearson correlation coefficients (r2) for these relationships ran-ged between 0.12 and 0.40. In contrast, the relationships for thePCBs by SPME (p = 0.44; r2 = 0.21; n = 30) and OCs by PED(p = 0.067; r2 = 0.12; n = 29) were not statistically significant. Thedetectability of PCBs at sub ng/L concentrations by SPME is limited,resulting in a lower number of matched data points and a likelyhigher uncertainty in the aqueous concentrations reported near/at the congener-specific MDL. The estimated aqueous concentra-tions for dieldrin fell well below the trend lines for both PSDs(more so for PEDs), suggesting a lower bioaccumulative potentialcompared with the other OC analytes. Even so, the PED-tissue rela-tionship for OCs was marginally significant. PBDEs were observedin extremely low concentrations over a relatively narrow concen-tration range and thus are not shown. Taken together, these resultsindicate that both types of PSDs represent the bioaccumulation po-tential of the targeted hydrophobic chemicals.
Of the 40 common analytes measured in both tissues and POCIS,only diphenhydramine was detected in both matrices at a commonsite (Fig. 4). Concentrations of diphenhydramine ranged from 0.1and 0.03 ng/L at SFYB and LARM, respectively, compared to musselconcentrations of 0.24 and 0.25 ng/g (dry weight). In most cases,the chemicals detected in the mussels had log Kows > 3 indicatinga greater potential to bioconcentrate whereas chemicals detectedin the POCIS had logKows < 3 which is consistent with the predictedperformance of the sampler (Alvarez et al., 2007).
Phosphate flame retardants (PFRs) were detected in high con-centrations in POCIS ranging from a mean of 1.2 ng/L (triphenylphosphate) to 930 ng/L (TDCPP), but were not detected in tissuesfrom any site. Information on the accumulation of PFRs in musseltissue is limited. Green et al. (2008) reported measuring TCEP
Please cite this article in press as: Alvarez, D.A., et al. Occurrence of contaminansampling devices. Mar. Pollut. Bull. (2013), http://dx.doi.org/10.1016/j.marpolb
(23 lg/kg wet weight) in blue mussels from only one site in Nor-wegian waters compared to relatively high concentrations in allsediment samples collected during the study. Bioconcentrationfactors (BCFs) of PFRs in mussels are unknown; however, measure-ments have been made in common carp (Cyprinus carpio) for TCEP(0.6–0.8 L/kg), TDCPP (0.3–3.3 L/kg), and TCPP (0.8–2.8 L/kg) indi-cating the potential for bioconcentration albeit low in many cases(Verbruggen et al., 2005). Potentially lower lipid levels in musselsthan in carp may also result in lower BCF values, thereby reducingthe likelihood of detecting PFRs in mussel tissue.
4. Conclusions
In this study, three PSDs were used to sample a diverse set ofanthropogenic organic chemicals in the coastal waters of San Fran-cisco Bay and the Southern California Bight. The distribution ofchemicals across sites was broad preventing linking chemicaloccurrence to the land-use characteristics of the site. However,when comparing the abundance of individual chemicals at eachsite, there was a distinction between the sites located in the SFBay area and the SCB.
Comparison of the three PSDs used in this study indicated thatthe most information on the presence of organic contaminants inthe watershed would be obtained by using a combination of thesamplers. Differences between the PED and SPME were minor withthe exception of the amount of chemical sampled for detection.Combined with the POCIS, data on chemicals with a wide rangeof Kows can be measured.
The data from the PSD/mussel tissue comparison clearly showsthat while use of biota for contaminant monitoring programs isuseful for PBTs, it can be extremely limited in the ability to detectmost of the hydrophilic CECs. PSDs such as the POCIS provide ameans of measuring CECs at low, but potentially toxicologically
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relevant concentrations. The data does not suggest that onemonitoring technique should be used exclusively. Instead, the dif-ferent types of PSDs and incorporation of tissue analyses should beconsidered as complementary techniques, each providing a uniquepicture of chemical occurrence in the environment.
Acknowledgements
The authors thank D. Diehl, D. Tsukada and P. Salop for deploy-ment and retrieval of PSDs. This study was funded in part by amemorandum of agreement (MOA-2008-061(Amend 004)/8099)between the USGS and NOAA’s National Ocean Service.
Any use of trade, firm, or product names is for descriptive pur-poses only and does not imply endorsement by the U.S. Government.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, inthe online version, at http://dx.doi.org/10.1016/j.marpolbul.2013.04.022.
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