Kenneth C. Schiff

IRON AS A REFERENCE ELEMENT FOR DETERMINING TRACE METAL ENRICHMENT IN SOUTHERN CALIFORNIA COASTAL SHELF SEDIMENTS

Abstract Major and trace elements occur naturally in the environment at levels which are detectable by most ocean monitoring programs. This natural occurrence of metals in the environment complicates assessments of potentially contaminated marine sediments because measurable quantities of metals do not automatically infer anthropogenic enrichment. In this study, we use iron as a conservative tracer to differentiate natural from anthropogenic components of bulk sediment metal concentrations in the Southern California Bight (SCB). Baseline relationships between iron and eight trace metals were established using data from non-impacted sites distant from known point and non-point sources of pollution. These baseline relationships were evaluated for geographic, depth, and analytical variance, and then were validated using an independent data set. Using the reference element technique, we determined that over half of the 248 SCB sites measured were enriched in at least one trace metal. All trace metals investigated showed some level of enrichment: silver, cadmium, and chromium showed the greatest sediment enrichment, while arsenic and nickel showed the least enrichment. Degrees of enrichment were unevenly distributed throughout the SCB. Trace metal contamination was extensive in the Santa Monica Bay where approximately 80% of the sites were contaminated by more than three metals.

Water quality indicators and the risk of illness at beaches with nonpoint sources of fecal contamination.

Background: Indicator bacteria are a good predictor of illness at marine beaches that have point sources of pollution with human fecal content. Few studies have addressed the utility of indicator bacteria where nonpoint sources are the dominant fecal input. Extrapolating current water-quality thresholds to such locations is uncertain. Methods: In a cohort of 8797 beachgoers at Mission Bay, California, we measured baseline health at the time of exposure and 2 weeks later. Water samples were analyzed for bacterial indicators (enterococcus, fecal coliforms, total coliforms) using both traditional and nontraditional methods, ie, chromogenic substrate or quantitative polymerase chain reaction. A novel bacterial indicator (Bacteroides) and viruses (coliphage, adenovirus, norovirus) also were measured. Associations of 14 health outcomes with both water exposure and water quality indicators were assessed. Results: Diarrhea and skin rash incidence were the only symptoms that were increased in swimmers compared with nonswimmers. The incidence of illness was not associated with any of the indicators that traditionally are used to monitor beaches. Among nontraditional water quality indicators, associations with illness were observed only for male-specific coliphage, although a low number of participants were exposed to water at times when coliphage was detected. Conclusions: Traditional fecal indicators currently used to monitor these beaches were not associated with health risks. These results suggest a need for alternative indicators of water quality where nonpoint sources are dominant fecal contributors.

Multitiered Approach Using Quantitative PCR To Track Sources of Fecal Pollution Affecting Santa Monica Bay, California

ABSTRACT The ubiquity of fecal indicator bacteria such as Escherichia coli and Enterococcus spp. in urban environments makes tracking of fecal contamination extremely challenging. A multitiered approach was used to assess sources of fecal pollution in Ballona Creek, an urban watershed that drains to the Santa Monica Bay (SMB) near Los Angeles, Calif. A mass-based design at six main-stem sites and four major tributaries over a 6-h period was used (i) to assess the flux of Enterococcus spp. and E. coli by using culture-based methods (tier 1); (ii) to assess levels of Enterococcus spp. by using quantitative PCR and to detect and/or quantify additional markers of human fecal contamination, including a human-specific Bacteroides sp. marker and enterovirus, using quantitative reverse transcriptase PCR (tier 2); and (iii) to assess the specific types of enterovirus genomes found via sequence analysis (tier 3). Sources of fecal indicator bacteria were ubiquitous, and concentrations were high, throughout Ballona Creek, with no single tributary dominating fecal inputs. The flux of Enterococcus spp. and E. coli averaged 109 to 1010 cells h−1 and was as high at the head of the watershed as at the mouth prior to discharge into the SMB. In addition, a signal for the human-specific Bacteroides marker was consistently detected: 86% of the samples taken over the extent during the study period tested positive. Enteroviruses were quantifiable in 14 of 36 samples (39%), with the highest concentrations at the site furthest upstream (Cochran). These results indicated the power of using multiple approaches to assess and quantify fecal contamination in freshwater conduits to high-use, high-priority recreational swimming areas.

Water quality impacts of stormwater discharges to Santa Monica Bay

Urban stormwater runoff is a major source of contaminants to southern Californias coastal waters, yet little is known about the fate and effects of these discharges. A 3-year multidisciplinary project was conducted to investigate the dispersion of stormwater plumes in Santa Monica Bay and the resultant impacts on the water column and benthos. This paper describes the toxicity component of the study. Sea urchin fertilization toxicity tests were conducted on stormwater from the two largest discharges into the bay: Ballona Creek, which drains a highly urbanized watershed, and Malibu Creek, which receives runoff from a largely undeveloped watershed. Every sample of Ballona Creek stormwater tested was toxic (usually >5 toxic units), while Malibu Creek stormwater had a lower frequency and magnitude of toxicity (usually <4 toxic units). Surface water samples collected within the Ballona Creek stormwater discharge plume were always toxic whenever the concentration of stormwater in the plume exceeded 10%. The toxic portion of the Ballona Creek stormwater plume extended more than 4 km offshore on one occasion. Toxicity identification studies indicated that zinc was the primary cause of toxicity in both Ballona Creek stormwater and the discharge plume. No acute sediment toxicity (10-day amphipod survival) was present in the study area, although interstitial water toxicity was present at some stations located near the mouth of Ballona Creek. Differences in watershed characteristics likely were responsible for the greater toxicity of the Ballona Creek stormwater discharge plume. The Ballona Creek watershed contained a greater degree of urbanization (83% versus 12% for Malibu Creek) and the presence of a network of concrete flood control channels resulted in a stormwater plume containing elevated concentrations of toxins that received less initial dilution (compared to Malibu Creek) in the nearshore environment.

Watershed‐based sources of polycyclic aromatic hydrocarbons in urban storm water

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic and mutagenic compounds, ubiquitous in the air and water of urban environments, and have been shown to accumulate in coastal estuarine and marine sediments. Although previous studies have documented concentrations and loads of PAHs in urban runoff, little is known about the sources and temporal patterns of PAH loading from storm water. This study characterized the sources and temporal patterns of PAHs in urban storm water by analyzing PAH concentrations and loads from a range of homogeneous land use sites and in-river mass emission sites throughout the greater Los Angeles, California, USA, region. Samples were collected at 30- to 60-min intervals over the course of a storm during multiple storm events over a four-year period in order to investigate PAH sources and inter- and intrastorm patterns in loading. Polycyclic aromatic hydrocarbon storm fluxes ranged from 1.3 g/km2 for the largely undeveloped Arroyo Sequit watershed to 223.7 g/km2 for the highly urbanized Verdugo Wash watershed, with average storm fluxes being 46 times higher in developed versus undeveloped watersheds. Early-season storms repeatedly produced substantially higher loads than comparably sized late-season storms. Within individual storms, PAHs exhibited a moderate first flush with between 30 and 60% of the total PAH load being discharged in the first 20% of the storm volume. The relative distribution of individual PAHs demonstrated a consistent predominance of high-molecular-weight compounds indicative of pyrogenic sources.

Using rapid indicators for Enterococcus to assess the risk of illness after exposure to urban runoff contaminated marine water

BACKGROUNDnTraditional fecal indicator bacteria (FIB) measurement is too slow (>18 h) for timely swimmer warnings.nnnOBJECTIVESnAssess relationship of rapid indicator methods (qPCR) to illness at a marine beach impacted by urban runoff.nnnMETHODSnWe measured baseline and two-week health in 9525 individuals visiting Doheny Beach 2007-08. Illness rates were compared (swimmers vs. non-swimmers). FIB measured by traditional (Enterococcus spp. by EPA Method 1600 or Enterolert™, fecal coliforms, total coliforms) and three rapid qPCR assays for Enterococcus spp. (Taqman, Scorpion-1, Scorpion-2) were compared to health. Primary bacterial source was a creek flowing untreated into ocean; the creek did not reach the ocean when a sand berm formed. This provided a natural experiment for examining FIB-health relationships under varying conditions.nnnRESULTSnWe observed significant increases in diarrhea (OR 1.90, 95% CI 1.29-2.80 for swallowing water) and other outcomes in swimmers compared to non-swimmers. Exposure (body immersion, head immersion, swallowed water) was associated with increasing risk of gastrointestinal illness (GI). Daily GI incidence patterns were different: swimmers (2-day peak) and non-swimmers (no peak). With berm-open, we observed associations between GI and traditional and rapid methods for Enterococcus; fewer associations occurred when berm status was not considered.nnnCONCLUSIONSnWe found increased risk of GI at this urban runoff beach. When FIB source flowed freely (berm-open), several traditional and rapid indicators were related to illness. When FIB source was weak (berm-closed) fewer illness associations were seen. These different relationships under different conditions at a single beach demonstrate the difficulties using these indicators to predict health risk.

Watershed and land use–based sources of trace metals in urban storm water

Trace metal contributions in urban storm water are of concern to environmental managers because of their potential impacts on ambient receiving waters. The mechanisms and processes that influence temporal and spatial patterns of trace metal loading in urban storm water, however, are not well understood. The goals of the present study were to quantify trace metal event mean concentration (EMC), flux, and mass loading associated with storm water runoff from representative land uses; to compare EMC, flux, and mass loading associated with storm water runoff from urban (developed) and nonurban (undeveloped) watersheds; and to investigate within-storm and within-season factors that affect trace metal concentration and flux. To achieve these goals, trace metal concentrations were measured in 315 samples over 11 storm events in five southern California, USA, watersheds representing eight different land use types during the 2000 through 2005 storm seasons. In addition, 377 runoff samples were collected from 12 mass emission sites (end of watershed) during 15 different storm events. Mean flux at land use sites ranged from 24 to 1,238, 0.1 to 1,272, and 6 to 33,189 g/km(2) for total copper, total lead, and total zinc, respectively. Storm water runoff from industrial land use sites contained higher EMCs and generated greater flux of trace metals than other land use types. For all storms sampled, the highest metal concentrations occurred during the early phases of storm water runoff, with peak concentrations usually preceding peak flow. Early season storms produced significantly higher metal flux compared with late season storms at both mass emission and land use sites.

Assessment of efficient sampling designs for urban stormwater monitoring.

Monitoring programs for urban runoff have not been assessed for effectiveness or efficiency in estimating mass emissions. In order to determine appropriate designs for stormwater, total suspended solids (TSS) and flow information from the Santa Ana River was collected nearly every 15 min for every storm of the 1998 water year. All samples were used to calculate the true load and then three within-storm sampling designs (flow-interval, time-interval, and simple random) and five among-storm sampling designs (stratified by size, stratified by season, simple random, simple random of medium and large storms, and the first m storms of the season) were simulated. Using these designs, we evaluated three estimators for storm mass emissions (mean, volume-weighted, and ratio) and three estimators for annual mass emissions (median, ratio, and regular). Designs and estimators were evaluated with respect to accuracy and precision. The optimal strategy was used to determine the appropriate number of storms to sample annually based upon confidence interval width for estimates of annual mass emissions and concentration. The amount of detectable trend in mass emissions and concentration was determined for sample sizes 3 and 7. Single storms were most efficiently characterized (small bias and standard error) by taking 12 samples following a flow-interval schedule and using a volume-weighted estimator of mass emissions. The ratio estimator, when coupled with the simple random sample of medium and large storms within a season, most accurately estimated concentration and mass emissions; and had low bias over all of the designs. Sampling seven storms is the most efficient method for attaining small confidence interval width for annual concentration. Sampling three storms per year allows a 20% trend to be detected in mass emissions or concentration over five years. These results are decreased by 10% by sampling seven storms per year.

Impacts of stormwater discharges on the nearshore benthic environment of Santa Monica Bay.

Although large loads of potentially toxic constituents are discharged from coastal urban watersheds, very little is known about the fates and eventual impacts of these stormwater inputs once they enter the ocean. The goal of this study was to examine the effects of stormwater discharges on the benthic marine environment of Santa Monica Bay. Sediment samples were collected across a gradient of stormwater impact following significantly sized storm events offshore Ballona Creek (a predominantly developed watershed) and Malibu Creek (a predominantly undeveloped watershed). Sediments offshore Malibu Creek had a greater proportion of fine-grained sediments, organic carbon, and naturally occurring metals (i.e., aluminum and iron), whereas sediments offshore Ballona Creek had higher concentrations of anthropogenic metals (i.e., lead) and organic pollutants (i.e., total DDT, total PCB, total PAH). The accumulation of anthropogenic sediment contaminants offshore Ballona Creek was evident up to 2 km downcoast and 4 km upcoast from the creek mouth and sediment concentrations covaried with distance from the discharge. Although changes in sediment texture, organic content, and an increase in sediment contamination were observed, there was little or no alteration to the benthic communities offshore either Ballona or Malibu Creek. Both sites were characterized as having an abundance, species richness, biodiversity and benthic response index similar to shallow water areas distant from creek mouths throughout the Southern California Bight. There was not a preponderance of pollution tolerant, nor a lack or pollution sensitive, species offshore either creek mouth.

Sediment Chemistry on the Mainland Shelf of the Southern California Bight

Abstract To understand large-scale environmental changes and the cumulative effects of multiple discharges, 248 sites on the mainland shelf of the Southern California Bight (SCB) were sampled using a stratified-random study design. Eighty-nine per cent of SCB sediments were found to contain evidence of anthropogenic contamination. Eighty-nine per cent of the SCB was contaminated with chlorinated hydrocarbons including total DDT (82%) and total PCB (46%). Using iron as a conservative tracer of natural contributions for eight metals of interest, 50% of the SCB was estimated to be anthropogenically enriched in at least one trace metal. Sediments near discharges from publicly owned treatment works (POTWs) and urbanized watersheds had a greater extent and magnitude of contamination than other SCB sediments. Santa Monica Bay, where numerous anthropogenic sources commingle, had significantly higher concentrations of every constituent examined relative to other regions of the SCB.