Nitromusk compounds in San Francisco Bay sediments

Synthetic nitromusk fragrances are used in a wide variety of consumer products and can enter aquatic environments through wastewater effluent. Although nitromusks are known to be hydrophobic, little attention has been paid to their behavior in sediments. A sediment extraction method using sonication was developed and used to analyze samples from San Francisco Bay. Both musk xylene (MX) and musk ketone (MK) were found at low levels, with mean concentrations of 0.034 and 0.038ngg(-1), respectively. The highest concentrations were found in the southernmost region of the Bay. Samples were also analyzed from a nearby tidal channel fed by a wastewater treatment plant outfall. At this location both musk xylene and musk ketone were found at higher concentrations of 0.13-0.24ngg(-1) MX and 1.08-2.74ngg(-1) MK. A metabolite of musk xylene was also found at levels up to 4.08ngg(-1), suggesting that these metabolites may play an important role in the fate of nitromusk compounds. Concentrations of all three compounds were highest at the earliest of four sampling dates, and a geographic survey of sediments along the tidal channel showed that concentrations decreased rapidly with distance from the outfall and were close to background before the channel reached the Bay.     

Mercury in San Francisco Bay forage fish

In the San Francisco Estuary, management actions including tidal marsh restoration could change fish mercury (Hg) concentrations. From 2005 to 2007, small forage fish were collected and analyzed to identify spatial and interannual variation in biotic methylmercury (MeHg) exposure. The average whole body total Hg concentration was 0.052 μg g⁻¹ (wet-weight) for 457 composite samples representing 13 fish species. MeHg constituted 94% of total Hg. At a given length, Hg concentrations were higher in nearshore mudflat and wetland species (Clevelandia ios, Menidia audens, and Ilypnus gilberti), compared to species that move offshore (e.g., Atherinops affinis and Lepidogobius lepidus). Gut content analysis indicated similar diets between Atherinops affinis and Menidia audens, when sampled at the same locations. Hg concentrations were higher in sites closest to the Guadalupe River, which drains a watershed impacted by historic Hg mining. Results demonstrate that despite differences among years and fish species, nearshore forage fish exhibit consistent Hg spatial gradients.     

A PAH fate model for San Francisco Bay

A mass balance model was applied to simulate the long-term fate of PAHs in San Francisco Bay. The model treats the Bay as a single box with interacting water and sediment compartments, and includes loading, volatilization, outflow to the ocean, degradation, and burial in deep sediment. The estimated time required for loss of one-half of the mass in the Bay in the absence of loading ranged from 20 d for naphthalene to 5 yr for benzo(b)fluoranthene. Uncertainty analysis using Monte Carlo simulation indicated a high degree of influence and uncertainty for degradation rates, suggesting that improved estimates of degradation would significantly improve the predictive ability of the model. A comparison of model calculations to literature values suggested that external PAH loading to San Francisco Bay was at or above previous estimates of 3600 kgyr(-1), and that degradation in the Bay was within the range of commonly published estimates for high molecular weight PAHs (4.0 x 10(-5) to 4.0 x 10(-4)d(-1)).     

Polychlorinated biphenyl spatial patterns in San Francisco Bay forage fish

Industrialized waterways frequently contain nearshore hotspots of legacy polychlorinated biphenyl (PCB) contamination, with uncertain contribution to aquatic food web contamination. We evaluated the utility of estuarine forage fish as biosentinel indicators of local PCB contamination across multiple nearshore sites in San Francisco Bay. Topsmelt (Atherinops affinis) or Mississippi silverside (Menidia audens) contamination was compared between 12 targeted sites near historically polluted locations and 17 probabilistically chosen sites representative of ambient conditions. The average sum of 209 PCB congeners in fish from targeted stations (441 ± 432 ng g^?1 wet weight, mean ± SD) was significantly higher than probabilistic stations (138 ± 94 ng g^?1). Concentrations in both species were comparable to those of high lipid sport fish in the Bay, strongly correlated with spatial patterns in sediment contamination, and above selected literature thresholds for potential hazard to fish and wildlife. The highest concentrations were from targeted Central Bay locations, including Hunter’s Point Naval Shipyard (1347 ng g^?1; topsmelt) and Stege Marsh (1337 ng g^?1; silverside). Targeted sites exhibited increased abundance of lower chlorinated congeners, suggesting local source contributions, including Aroclor 1248. These findings indicate that current spatial patterns in PCB bioaccumulation correlate with historical sediment contamination due to industrial activity. They also demonstrate the utility of naturally occurring forage fish as biosentinels of localized PCB exposure.     

PBDEs in the San Francisco Bay Area: measurements in harbor seal blubber and human breast adipose tissue

To explore the levels of polybrominated diphenyl ethers (PBDEs) in California, samples from 11 archived harbor seals (Phoca vitulina Richardsi) from the San Francisco Bay and breast adipose tissue samples from 23 women were analyzed. The levels of PBDEs in human tissue samples were in the low ng/g fat range, with PBDEs 47, 153, 154, 99, and 100 as the major congeners. Average sigma PBDEs (86 ng/g fat) in these California women are the highest human levels reported to date. An inverse relationship between concentration of PBDEs and age of these women was apparent. The levels of PBDEs measured in harbor seal blubber were in the low ng/g to low microg/g fat range, with the same major congeners as those measured in the human tissues. PBDE 47 was the highest among all congeners measured in both human tissue and seal blubber samples. The concentrations of PBDEs in harbor seals in the San Francisco Bay have increased dramatically over the past decade, with current levels among the highest reported for this species.     

Comparisons of EPA Rollback,Empirical/Kinetic,and Physicochemical Oxidant Prediction Relationships in the San Francisco Bay Area

This paper describes, compares and evaluates selected Oxidant Prediction Relationships {OPRs) in terms of projections of hydrocarbon emission reductions required for attainment of the former 0.08 ppm standard and the new 0.12 ppm standard in the San Francisco Bay Area in 1985. The OPRs analyzed are the LIRAQ physicochemical model, EPA’s Empirical Kinetic Modeling Approach (EKMA), linear and Appendix J rollback, and an empirical OPR based on local observations.

LIRAQ simulations indicated that to achieve the 0.12 ppm ozone standard, 1985 hydrocarbon emissions must be reduced by 27% from projected levels. The equivalent reductions derived from simple linear rollback, linear rollback with 0.04 ppm background, and the local empirical OPR were 32%, 45% and 37%, respectively. The LIRAQ simulations also showed that reduction of both hydrocarbon and NO_x emissions is less effective than reduction of hydrocarbons only. The attempt to apply EKMA failed because the Bay Area’s low hydrocarbon/NO_x ratios and observed ozone levels are not consistent with the standard EKMA isopleth curves.

For planning, proper OPR selection is important because the wide range in the projections of various OPRs translates into a correspondingly wide range in control costs. Physicochemical OPRs are preferred because they are verifiable; they account for complex topography, meteorology, and source distributions; and because they can treat a variety of control strategies. In the future, the uncertainties associated with the projections can be resolved by assessing trends in air quality on a regular basis and by upgrading and reapplying the prediction methodologies as new information becomes available.     

The Effect of Rapid Transit on San Francisco Bay Air Quality

Classical procedures for the microdetermination of fluoride in vegetation are extremely time consuming. They generally involve ashing, fusion with alkali, distillation, and finally fluoride estimation. Sample size requirements for such procedures are on the order of a gram or more, making the procedure useless for determining low fluoride concentrations in small samples. A procedure for micro-fluoride determination in vegetation is proposed which utilizes the oxygen flask combustion technique (Schoniger flask). The gaseous products of combustion are absorbed in 10.0 ml of 0.05N sodium hydroxide containing 1.00 µg of fluoride. The analysis of the fluoride is performed directly on the absorption solution after addition of a combination complexing-buffer solution, using a specific fluoride ion electrode. The sensitivity of the electrode is such that 0.2 µg of fluoride can be easily detected in this volume. Added oxidant was required in the combustion step for some vegetation samples to completely free the fluoride from its organic matrix. Comparisons with the standard Willard-Winter procedure gave excellent results. Combustion of sodium fluoride standards as well as submicrogram quantities of a fluoro-organic compound showed recoveries greater than 90%. The direct combustion, coupled with fluoride ion electrode determination, reduces analysis time drastically. A complete analysis can be performed in 1/2 hr, with a minimum amount of equipment.     

Investigation to Determine the Possible Need for a Regulation on Organic Compound Emissions from Stationary Sources in the San Francisco Bay Area

The problem of an investigation of the need for a regulation on organic compound emissions in the San Francisco Bay Area can be divided into two major areas: 1. Is there a need for a regulation on organic compound emissions? What is the extent of photochemical smog effects? How much control is necessary to achieve the desired effects?

2. (2) If the need exists for an organic compound regulation, can a performance type regulation be written for all types of organic compound emissions? Must the regulation be directed toward specific industries or types of emissions? Can the regulation be adequately enforced—both practically and legally?

This paper will describe the studies undertaken by the District Staff to answer the first set of questions. Work covering the second group of questions is now under investigation.     

Preparation and Use of Spatially and Temporally Resolved Emission Inventories in the San Francisco Bay Region

Three regional agencies recently prepared an Air Quality Maintenance Plan for the San Francisco Bay Area oxidant problem. An Eulerian, photochemical model, LIRAQ, provided the technical basis for the plan recommendations. A major LIRAQ input is an emission inventory accurately resolved to one kilometer and one hour increments. The cooperating agencies prepared such inventories, covering 20,000 sq km, for one base and two future years. Several manual and computer-assisted techniques were developed to utilize a variety of independent data bases. Population, land use, employment and transportation data were oganized into a common system of coordinates and units to produce the needed spatial input. Estimates of hourly variation were made by source category based on production rates, fuel use, traffic patterns, flight schedules, and other factors. The result was a series of consistent, detailed inventories which provide a powerful air quality modeling and planning tool. The detail is attained at considerable expense, but the cost is easily justifiable when compared to implementation costs for control strategies.     

Seasonal variations and trends in concentrations of filter-collected polycyclic aromatic hydrocarbons (PAH) and mutagenic activity in the San Francisco Bay area

Air monitoring in the San Francisco Bay Area was carried out to measure outdoor community air concentrations of polycyclic aromatic hydrocarbons (PAH) and mutagenic activity (mutagenicity) in particulate organic matter (POM). Monitoring began in 1979 and is currently conducted at six stations. PAH and mutagenicity tests were performed on organic extracts prepared from high volume (hi-vol) filters composited every four months, by meterological season. PAH were determined by high pressure liquid chromatography (HPLC) with fluorescence and ultraviolet detection. Mutagenicity was measured in the Ames Salmonella bioassay using strain TA98 with and without metabolic activation. The nine-year mean concentration of benzo(a)pyrene (BaP) was 0.4 ng/m3. The mutagenicity of this amount of BaP accounted for only about 0.2% of the observed mutagenicity in POM and other measured PAH accounted for even less. Concentrations of PAH and mutagenicity were three to nine times higher during the winter than during other seasons. Year-to-year wintertime trends in several PAH were also seen. Early in the 1980s, winter concentrations of BaP and benzo (g,h,i)perylene increased. However since the mid-1980's, their concentrations have fallen. The decrease in PAH concentrations may be the result of an increasing proportion of vehicles with relatively low organic emissions. In contrast to PAH, mutagenicity did not show significantly year-to-year time trends.     

Mercury burdens in Chinese mitten crabs (Eriocheir sinensis) in three tributaries of southern San Francisco Bay, California, USA

Chinese mitten crabs (Eriocheir sinensis), endemic to Asia, were first reported in the San Francisco Bay in 1992. They are now established in nearly all San Francisco Bay tributaries. These crabs accumulate more metals, such as mercury, than crustaceans living in the water column. Because their predators include fish, birds, mammals and humans, their mercury burdens have an exceptional potential to impact the ecosystem and public health. We sought to elucidate the potential threat of mitten crab mercury burdens in three adjacent streams in southern San Francisco Bay, one of which is known to be contaminated with mercury. Mitten crabs had hepatopancreas concentrations of total mercury and methylmercury that did not differ among streams. The maximum burden we measured was below the action level of 1 ppm recommended by the USEPA. Hepatopancreas concentrations of methylmercury declined with increasing crab size, suggesting a mechanism for mercury excretion and that predators might reduce mercury exposure if they select larger crabs. Because mercury may be heterogeneously distributed among tissues, estimation of the impacts of crab mercury burdens on the environment requires more data on the feeding preferences of predators.     

Atmospheric Tracer Techniques and Gas Transport in the Primary Aluminum Industry

The results of 35 Individual SF₆ tracer tests conducted in Norway during 1978 demonstrate the applicability of tracer techniques to the study of a wide variety of pollutant transport problems found in the primary aluminum industry. Tracer methods were employed to determine the efficiency of the pollutant control system over a single reduction cell under a variety of operating conditions. Two tests conducted during normal operation gave efficiencies equal to 100 ±19% and 79 ± 12%, while a test performed during the occurrence of an anode effect yielded an efficiency equal to 66 ± 22%.

Tracer investigations of flow in the wake of a smelter hall indicated that between 1 % and 11 % of secondary, roof-top emissions can become entrained in the recirculation cavity and reenter the hall through the ventilation fresh air supply. These reentry rates were observed for release heights as high as 8 m above the existing roof exhaust duct. Tracer dispersion data collected within 20 building heights of the smelter agreed very well with extrapolations of McEIroy- Pooler dispersion curves for an urban area. Dispersion curves determined from a previous wind tunnel study of flow downwind of an isolated building underestimated dispersion downwind of the vs.melter complex.

The total fluoride mass flow rate measured downwind of a smelter during wet, foggy conditions indicated that wet removal rates of fluorides are in the range 3.2 × 10^?4/s to 6.4 × 10^?4/s. Simulation of the source with several tracer point releases and simultaneous measurement of fluoride and tracer ground-level concentrations downwind of the smelter eliminated the need for measurements of vertical profiles of wind speed and fluoride concentration during the experiment.     

Smog Chamber Simulation of Los Angeles Pollutant Transport

The body of information presented in this paper is directed to those individuals concerned with the effect of urban pollution on downwind areas. In the absence of any evidence, it has been widely assumed that increasing NO _x emissions have caused oxidant levels to increase downwind of Los Angeles, i.e., Riverside and San Bernardino. This smog chamber study simulated pollutant transport from Los Angeles to the downwind areas by irradiating a typical Los Angeles hydrocarbon/NO _x mixture for extended periods of time. The smog chamber experiments were extended to 22 hours to obtain an integrated light intensity equal to that which occurs in the Los Angeles area. The effects of variations of nitrogen oxide emissions on an aged air mass were examined. The results show that downwind oxidant levels are only slightly affected by large changes in NO _x emissions. However, it is clear that reduced nitrogen oxide emissions will lead to an increase in oxidant in downtown Los Angeles.     

Pollutant Transport During a Regional O3 Episode in the Mid-Atlantic States

ABSTRACT

Ozone (O₃) concentrations in the Baltimore-Washington (B-W) metropolitan area frequently exceed the National Ambient Air Quality Standard (NAAQS) in the summer months. The most extreme O₃ events occur in multi-day high O₃ episodes.¹ These events can be regional in scale, with O₃ concentrations exceeding the NAAQS at numerous locations along the eastern U.S. seaboard, and are typically associated with slow-moving or stagnant high pressure systems.^2-5 In the B-W region, the most extreme events typically occur with surface high pressure overhead or just west of the region and an upper air high-pressure area (ridge) to the west or northwest.¹ Besides providing conditions conducive to local O₃ production (subsidence and strong low-level inversions, weak horizontal winds, little cloud cover), this weather pattern may also result in transport of O₃ and its precursors from heavily industrialized areas west and north of the B-W region. In this paper, observations and back trajectories made during the severe regional O₃ event of July 12-15, 1995, are used to confirm the hypothesis that significant regional-scale transport of O₃ and its precursors occur during extreme O₃ events of the standard type in the B-W area.     

Weekday-Weekend Pollutant Studies of the Los Angeles Basin

Pollutant data from the Los Angeles Basin were analyzed for weekday-weekend differences for the smog months of June through September 1972 and 1973. The pollutants investigated were oxidant, NO, NO₂, total hydrocarbons (HC), CO, and particulates. In order to maintain the diurnal variation, the concentration percentiles were calculated for each weekday and weekend hour.