Application of an Effects-Based Monitoring Strategy to Assess the Impact of Contaminants on Fish Health in an Urbanized Watershed.

Effects-based monitoring frameworks that combine the use of analytical chemistry with in vitro cell bioassays, as well as in vivo whole organism tests offer an integrative approach to broadly screen for chemical contaminants and link their presence with adverse effects on aquatic organisms. California (USA) is currently evaluating the use of such a framework to assess the impact of contaminants of emerging concern (CECs) on biota in urbanized rivers and other waterbodies. In the present study, the occurrence and effects of contaminants found in the Los Angeles River (Los Angeles County, CA, USA) were examined using analytical chemistry and in vitro and in vivo bioassays. Male fathead minnows were deployed in field-based exposure units and exposed to river water for 21 d. The 2 field sites (above Bull Creek [BLC] and below Glendale Water Reclamation Plant [GWR]) were selected based on their unique characteristics and different contaminant discharge sources. In addition, 2 control units (filtered city water and estrone-spiked water) were added to the experimental design. Chemical analyses revealed differences in abundance of CECs between the 2 field sites and the controls, with GWR having the highest number and concentrations of CECs and metals. Cell bioassays screening for estrogenic, glucocorticoid, progestin, and dioxin-like activities were near or below detection limits in all river water samples, indicating a low potential for endocrine-related toxicity and tissue damage. Cell bioassay results were corroborated by the in vivo analyses. Field-exposed fish exhibited no changes in plasma hormones (e.g., estradiol), vitellogenin, or gonad maturation, but gene biomarkers of chemical exposure (cytochrome p450 1A and metallothionein) were significantly elevated, confirming exposure of the fish to complex chemical mixtures. The results demonstrate the value of a tiered monitoring approach to assess the sublethal effects of chemical mixtures on aquatic life. Environ Toxicol Chem 2021;40:402-412. © 2020 SETAC.

Exchange of polycyclic aromatic hydrocarbons among the atmosphere, water, and sediment in coastal embayments of southern California, USA.

The present study investigated cross-media transport between both the sediment and the water column and between the water column and the atmosphere, to understand the role of each compartment as a source or a sink of polycyclic aromatic hydrocarbons (PAH) in southern California, USA, coastal waters. Concentrations of PAH were measured in the atmosphere, water column, and sediment at four water-quality-impaired sites in southern California: Ballona Creek Estuary, Los Angeles Harbor, Upper Newport Bay, and San Diego Bay. These concentrations were used to calculate site-specific sediment-water and atmosphere-water exchange fluxes. The net sediment-water exchange of total PAH (t-PAH) was positive, indicating that sediments were a source to the overlying water column. Furthermore, the net atmosphere-water exchange (gas exchange + dry particle deposition) of t-PAH was typically positive also, indicating the water column was a net source of PAH to the surrounding atmosphere through gas exchange. However, in all cases, the magnitude of the diffusive flux of PAH out of the sediments and into the water column far exceeded input or output of PAH through air/water exchange processes. These results demonstrate the potential importance of contaminated sediments as a source of PAH to the water column in coastal waters of southern California.

Extent and magnitude of copper contamination in marinas of the San Diego region, California, USA.

Marinas are areas of special water quality concern because of the potential for pollutant accumulation within their protected waters. Perhaps the largest contaminant source to marinas is antifouling paints that leach copper to prevent the growth of encrusting organisms on vessel bottoms. Very little monitoring of marinas is typically conducted despite the potential environmental risk, particularly in the San Diego region of California, USA where as many as 17,000 recreational vessels are berthed. The objective of this study was twofold: (1) determine the extent and magnitude of dissolved copper concentrations in marinas throughout the San Diego region, and (2) determine if elevated copper concentrations in marinas of the San Diego region are resulting in adverse biological impacts. A probabilistic study design was used to sample water column copper concentrations and toxicity (using Mytilus galloprovincialis) at 30 stations. Results indicated that exceedence of state water quality objectives was widespread (86% of marina area), but that toxicity was much less prevalent (21% of marina area). Toxicity identification evaluations (TIEs) conducted at the most toxic sites indicated that toxicity was largely due to trace metals, most likely copper. Toxicity was reduced using TIE treatments that chelated trace metals such as cation exchange column, ethylenediaminetetraacetic acid (EDTA), and sodium thiosulfate (STS). Moreover, increasing dissolved copper concentrations correlated with increasing toxicity and these copper concentrations were high enough to account for virtually all of the observed toxicity.

A passive sampler based on solid phase microextraction (SPME) for sediment-associated organic pollutants: Comparing freely-dissolved concentration with bioaccumulation.

The elevated occurrence of hydrophobic organic chemicals (HOCs) such as polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCBs) and legacy organchlorine pesticides (e.g. chlordane and DDT) in estuarine sediments continues to poses challenges for maintaining the health of aquatic ecosystems. Current efforts to develop and apply protective, science-based sediment quality regulations for impaired waterbodies are hampered by non-concordance between model predictions and measured bioaccumulation and toxicity. A passive sampler incorporating commercially available solid phase microextraction (SPME) fibers was employed in lab and field studies to measure the freely dissolved concentration of target HOCs (Cfree) and determine its suitability as a proxy for bioaccumulation. SPME deduced Cfree for organochlorines was highly correlated with tissue concentrations (Cb) of Macoma and Nereis spp. co-exposed in laboratory microcosms containing both spiked and naturally contaminated sediments. This positive association was also observed in situ for endemic bivalves, where SPME samplers were deployed for up to 1 month at an estuarine field site. The concordance between Cb and Cfree for PAH was more variable, in part due to likely biotransformation by model invertebrates. These results indicate that SPME passive samplers can serve as a proxy for bioaccumulation of sediment-associated organochlorines in both lab and field studies, reducing the uncertainty associated with model predictions that do not adequately account for differential bioavailability.

Copper emissions from antifouling paint on recreational vessels.

Trace metals, especially copper, are commonly occurring contaminants in harbors and marinas. One source of copper to these environs is copper-based antifouling coatings used on vessel hulls. The objective of this study was to measure dissolved copper contributions from recreational vessel antifouling coatings for both passive leaching and hull cleaning activities. To accomplish this goal, three coating formulations, including hard vinyl, modified epoxy and a biocide free bottom paint were applied on fiberglass panels and placed in a harbor environment. In situ measurements of passive leaching were made using a recirculating dome system. Monthly average flux rates of dissolved copper for the hard vinyl and modified epoxy coatings were 3.7 and 4.3 microg/cm(2)/day, respectively, while flux rates for the biocide free coating was 0.2 microg/cm(2)/day. The highest passive flux rates were measured initially after cleaning activities, rapidly decreasing to a baseline rate within three days, regardless of copper-based coating formulation. Hull cleaning activities generated between 8.6 and 3.8 microg dissolved copper/cm(2)/event for the modified epoxy and hard vinyl coatings, respectively. Aggressive cleaning using an abrasive product doubled the copper emissions from the modified epoxy coating, but produced virtually no change in the much tougher hard vinyl coating. When compared on a mass basis, roughly 95% of copper is emitted during passive leaching compared to hull cleaning activities over a monthly time period for a typical 9.1 m power boat.

Distribution and mass inventory of total dichlorodiphenyldichloroethylene in the water column of the southern California bight.

A large-scale survey on the area and depth stratified distribution of dichlorodiphenyltrichloroethane (DDT; mainly p,p'- and o,p'-dichlorodiphenyldichloroethylene (DDE)) contamination in the water column of the Southern California Bight (SCB) was conducted in 2003-2004 using a solid-phase microextraction-based sampling technique. Dissolved-phase DDEs were clearly widespread, with the central SCB containing the highest levels, and the Palos Verdes Shelf sediments have remained the dominant source of DDT compounds to the SCB. The p,p'- and o,p'-DDE concentrations ranged from < 0.073 to 2.6 ng/L and from < 0.043 to 0.26 ng/L, respectively, clearly elevated with respect to measured values from across the globe. DDEs were hypothesized to have been transported from the historically contaminated zone on the Palos Verdes Shelf to other areas via a repeated process of sediment resuspension/deposition and short-range advection. Total mass inventories were estimated at 14 and 0.86 kg for p,p'- and o,p'-DDE, respectively, for the sampled area, resulting in p,p'- and o,p'-DDE mass inventories for the entire SCB of 230 and 14 kg, respectively. Furthermore, total fluxes of p,p'-DDE were estimated to be in the range of 0.8 to 2.3 metric tons per year. These results suggest that the SCB has been and continues to be a significant source of DDT contamination to the global oceans.

Stormwater toxicity in Chollas Creek and San Diego Bay, California.

Stormwater discharges from Chollas Creek, a tributary of San Diego Bay, have been shown to be toxic to aquatic life. The primary objective of this study was to provide the linkage between in-channel measurements and potential impairments in the receiving waters of San Diego Bay. This study addressed this objective within the context of four questions: (1) How much area in San Diego Bay is affected by the discharge plume from Chollas Creek during wet-weather conditions?; (2) How much of the wet-weather discharge plume is toxic to marine aquatic life?; (3) How toxic is this area within the wet-weather discharge plume?; and (4) What are the constituent(s) responsible for the observed toxicity in the wet-weather plume? The stormwater plume emanating from Chollas Creek was dynamic, covering areas up to 2.25 km2. Approximately half of the plume was estimated to be toxic to marine life, based upon the results of purple sea urchin (Strongylocentroutus purpuratus) fertilization tests. The area nearest the creek mouth was the most toxic (NOEC = 3 to 12% plume sample), and the toxicity decreased with distance from the creek mouth. The toxicity of plume samples was directly proportional to the magnitude of plume mixing and dilution until, once outside the plume margin, no toxicity was observed. Trace metals, most likely zinc, were responsible for the observed plume toxicity based upon toxicity identification evaluations (TIEs). Zinc was also the constituent identified from in-channel samples of Chollas Creek stormwater using TIEs on the storms sampled in this study, and in storms sampled during the previous storm season.

Development of a solid-phase microextraction-based method for sampling of persistent chlorinated hydrocarbons in an urbanized coastal environment.

Solid-phase microextraction (SPME) has been used as an in situ sampling technique for a wide range of volatile organic chemicals, but SPME field sampling of nonvolatile organic pollutants has not been reported. This paper describes the development of an SPME-based sampling method employing a poly(dimethylsiloxane) (PDMS)-coated (100-microm thickness) fiber as the sorbent phase. The laboratory-calibrated PDMS-coated fibers were used to construct SPME samplers, and field tests were conducted at three coastal locations off southern California to determine the equilibrium sampling time and compare the efficacy of the SPME samplers with that of an Infiltrex 100 water pumping system (Axys Environmental Systems Ltd., Sidney, British Columbia, Canada). p,p'-DDE and o,p'-DDE were the components consistently detected in the SPME samples among 42 polychlorinated biphenyl congeners and 17 chlorinated pesticidestargeted. SPME samplers deployed attwo locations with moderate and high levels of contamination for 18 and 30 d, respectively, attained statistically identical concentrations of p,p'-DDE and o,p'-DDE. In addition, SPME samplers deployed for 23 and 43 d, respectively, at a location of low contamination also contained statistically identical concentrations of p,p'-DDE. These results indicate that equilibrium could be reached within 18 to 23 d. The concentrations of p,p'-DDE, o,p'-DDE, or p,p'-DDD obtained with the SPME samplers and the Infiltrex 100 system were virtually identical. In particular, two water column concentration profiles of p,p'-DDE and o,p'-DDE acquired by the SPME samplers at a highly contaminated site on the Palos Verdes Shelf overlapped with the profiles obtained by the Infiltrex 100 system in 1997. The field tests not only reveal the advantages of the SPME samplers compared to the Infiltrex 100 system and other integrative passive devices but also indicate the need to improve the sensitivity of the SPME-based sampling technique.