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.     

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.     

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)).     

Fluorescent Tracer Studies of Pollutant Transport in the San Francisco Bay Area

To simulate the transport and diffusion of airborne contaminants across a metropolitan region, point-source releases of fluorescent tracer material were made near various urban centers and some 50 samplers were arrayed in expected downwind directions. The effects of land-water, hill-valley, and urban-rural differences on airflow and diffusion were observed in their existing interrelationships during these experiments. Since the tracer could be assessed with high sensitivity over great distances, tracer results provided a quantitative indicator of pollutant dispersion across an extensive metropolitan complex.

From July 1967 through June 1968, the test series included typical seasonal weather patterns, with emphasis on those conducive to the travel and accumulation of pollutants. In each test about 15 kilograms of tracer material were released during two-hour periods, and significant dosages were found at downwind distances up to 80 kilometers. All tests were conducted during daylight hours, to coincide better with the oxidant-type pollution important in this region.

Dispersion characteristics showed much greater complexity than predictable from classical models, thus limiting the applicability of such models in this region. Built-up urban areas increased the initial dispersion rates of tracer clouds, and travel over water tended to decrease them. Hilly terrain resulted in increased dispersion, but channeling associated with such terrain caused locally higher concentrations. The complex horizontal dosage patterns obtained did confirm previously observed airflow patterns as aids in predicting pollutant distributions.     

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.     

Polychlorinated biphenyl congeners and organochlorine insecticides in the water column and sediments of Daya Bay, China.

Samples of sub-surface water, suspended particulate matter (SPM) and surface sediments collected from Daya Bay, China have been analysed for 12 polychlorinated biphenyl (PCB) congeners and 18 organochlorine insecticides, using gas chromatography electron capture detection. Total PCB levels varied from 91.1 to 1355.3 ng l-1 in water and from 0.85 to 27.37 ng g-1 dry weight in sediments. The levels of total organochlorine insecticides were in the range 143.3-5104.8 ng l-1 in water and 2.43-86.25 ng g-1 dry weight in sediment. None of the target compounds were detected in SPM. The levels of total hexachlorocyclohexanes in water varied from 35.5 to 1228.6 ng l-1, whilst in sediments they ranged from 0.32 to 4.16 ng g-1 dry weight. For the sum of dichlorodiphenyltrichloroethanes (DDTs), their levels were in the range 26.8-975.9 ng l-1 in water, and 0.14-20.27 ng g-1 dry weight in sediments. The distribution profiles of these contaminants in water and sediments suggest that there are a number of sources contributing to total contaminant burden in the bay, including soil runoffs, wastewater discharges, sewage outfalls and shipping activites. Ratios of DDT/(DDE + DDD) in the water and sediments indicate recent inputs of such chemicals into the day. The results, therefore, provide important information on the current contamination status of a key aquacultural area in China, and point to the need for urgent actions to stop the use of persistent agrochemicals such as DDT and lindane.     

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.     

Polychlorinated biphenyl residues in sandstorm depositions in Beijing, China

Sandstorms, which distribute many particles, are a special atmospheric occurrence and are frequent in northern China. We conducted this study to determine, for the first time, the concentration of polychlorinated biphenyls (PCBs) in sandstorm depositions. We collected 13 samples from urban areas of Beijing, and we measured a total of 144 PCB congeners. Thirteen samples all contained PCB residues. The total PCB concentration ranged from 1.6 to 15.6ngg(-1) (median, 4.8ngg(-1), dry weight), with trichlorinated biphenyls as the predominant homologue (>50.4%). Furthermore, we observed increasing PCB contamination from northwest to east Beijing. We later explored possible factors affecting contamination of the sandstorm depositions, which revealed a significant correlation between SigmaPCBs and the minimum particle size of the sandstorm deposition samples. Principal-component analysis revealed that the major source of PCBs in Beijing may be potentially associated with the number-one commercial PCB through the long-range transmission. In previous results, PCBs were not a severe component of contamination in sandstorm depositions of Beijing. However, this study suggested that sandstorm deposition may be a potential source of exposure to PCBs for the residents of Beijing, China.     

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.     

Polychlorinated biphenyls in Narragansett Bay surface sediments

Polychlorinated biphenyls (PCBs) were evaluated in 41 surface sediments collected from Narragansett Bay, RI in 1997-1998. Highest concentrations of total PCBs (1760 ng/g) were in rivers at the head of the bay and the values decreased southward toward the mouth of the bay, with elevated concentrations in some of the coves. The PCB levels in approximately 43% of the samples exceeded the effects range median (ERM) guideline [Environ. Manage. 19 (1995) 81] indicating possible adverse biological effects at these stations. Principal component analysis (PCA) of the surface sediment PCBs separated the Taunton River samples from the rest of the samples. This result suggests that this river has a different PCB composition and sources than the other areas investigated. It also showed that this river has a limited influence on other bay stations as the adjacent samples downstream did not have the same chemical signature. Congener ratios derived from the PCA were useful in distinguishing stations that had different sources of PCBs than the bulk of the bay sediments. Although Aroclor 1268 and 1270 accounted for <1% of all PCB production, their major components, CB206 and CB209, account for 3-6% of the CBs in most bay samples. This may reflect more local use of these Aroclor mixtures and/or be indicative of their relative stability, compared to less chlorinated mixtures. Using linear alkyl benzenes (LABs) as a marker for sewage derived PCBs suggested that up to 95% of the PCBs at the most contaminated sites in the Seekonk, Providence, and Taunton Rivers were sewage derived. This analysis also showed that there is a high background level (167 ng/g) of PCBs in the Seekonk and Providence River, while the Taunton River had a relatively low background level (23.7 ng/g). At the furthest stations south in the Providence River, the sewage derived PCBs only accounted for 23% of the total which suggests that PCB associated with sewage particles are rapidly deposited and are therefore not the most significant source of these compounds to the lower reaches of Narragansett Bay.     

Polychlorinated biphenyl, polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran residues in sediments and fish of the River Nile in the Cairo region

The levels of organohalogenated contaminants, i.e. PCBs, PCDDs and PCDFs were determined in sediment and fish samples collected from different locations in the River Nile, Egypt. Thirty-six sediment and eighteen fish samples were carried out during a period of 12 months from February 2003 to February 2004. Determination of PCBs and dioxins was carried out using a high resolution GC mass spectrometer. The results indicated that the PCB and PCDD/F mean concentrations in sediment samples ranged from 1461 to 2244 and from 240 to 775pgg(-1) dry wt basis, respectively. The mean concentration of PCBs and PCDD/Fs in fish samples were found to be in the range from 695 to 853pgg(-1) fresh wt for PCB congeners and from 27.7 to 121pgg(-1) lipid for total PCDD/Fs. Moreover, the concentrations of both PCBs and PCDD/Fs were found to be different at different locations along the River Nile. It could be concluded that the contamination of the River Nile is within the permissible limits set by the FDA and the Egyptian Standards for fish and shellfish.     

Polychlorinated biphenyl distribution and faecal excretion in rats fed wheat bran

Polychlorinated biphenyls (PCBs) are abundant and persistent environmental contaminants, which tend to accumulate through the food chain. Because of the toxic potential of these compounds, body burden should be kept as low as possible e.g. by taking dietary measures. In the present report, the effect of wheat bran consumption on absorption of dietary PCBs as well as on excretion of previously absorbed PCBs was investigated in rats. Moreover, the accumulation of 7 reference PCB congeners in liver and abdominal adipose tissue was studied. Faecal excretion of dietary PCBs was significantly higher in rats fed wheat bran compared to its placebo. As a result, apparent PCB digestibility was diminished, but not enough to significantly affect PCB accumulation in liver and abdominal adipose tissue. Furthermore, excretion of previously absorbed PCBs following switching of the rats to a control diet without added PCBs was enhanced by wheat bran fibre intake, although to a much lesser extent than excretion of PCBs originating directly from the diet. Consequently, stimulation of PCB clearance from liver and abdominal adipose tissue due to wheat bran consumption was not detectable. Although no preferential absorption of PCB congeners was observed, PCB patterns in tissues obviously differed from the dietary PCB pattern. This was mainly due to PCBs 52 and 101, which were metabolised in the body. Moreover, reduced levels of PCB 138 were found in liver, while PCB 28 and 138 were predominantly present in adipose tissue. The experiment also demonstrated that PCB redistribution from the liver to the adipose tissue occurs.     

Polychlorinated biphenyl and organochlorine insecticide residues in human adipose tissue in Poland

Concentrations of PCBs (polychlorinated biphenyls) and organochlorine insecticides such as DDT, HCHs (hexachlorocyclohexanes), HCB (hexachlorobenzene) and chlordanes were determined in human adipose fat from the provinces of Skierniewice and Gdańsk in Poland collected during 1979 and 1990, respectively. The mean levels (microg g(-1) lipid weight basis) in Skierniewice and Gdańsk were found to be 1.2+/-0.44 and 1.5+/-1.3 for PCBs, 25+/-16 and 15+/-13 for DDT, 0.53+/-0.17 and 0.25+/-0.09 for HCHs, 0.36+/-0.22 and 0.26+/-0.23 for HCB, and 0.11+/-0.08 and 0.07+/-0.04 for chlordanes, respectively. Very high concentrations of DDT were detected, with the maximum value as high as 52 microg g(-1) lipid weight in Skierniewice and 47 microg g(-1) lipid weight in Gdańsk. PCB residues contained in the human fat from Polish cadavers are comparable to those of the levels reported for industrialized nations. It is appraised from the levels of DDT and PCBs in Poles' fat that the Polish environment is still experiencing both types of contamination, arising from agricultural and industrial activities. Contamination of humans by other organochlorine insecticides was relatively lower.     

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.     

Polychlorinated biphenyl (118) activates osteoclasts and induces bone resorption in goldfish

To analyze the effect of polychlorinated biphenyl (PCB) 118 on fish bone metabolism, we examined osteoclastic and osteoblastic activities, as well as plasma calcium levels, in the scales of PCB (118)-injected goldfish. In addition, effect of PCB (118) on osteoclasts and osteoblasts was investigated in vitro. Immature goldfish, in which the endogenous effects of sex steroids are negligible, were used. PCB (118) was solubilized in dimethyl sulfoxide at a concentration of 10 ppm. At 1 and 2 days after PCB (118) injection (100 ng/g body weight), both osteoclastic and osteoblastic activities, and plasma calcium levels were measured. In an in vitro study, then, both osteoclastic and osteoblastic activities as well as each marker mRNA expression were examined. At 2 days, scale osteoclastic activity in PCB (118)-injected goldfish increased significantly, while osteoblastic activity did not change significantly. Corresponding to osteoclastic activity, plasma calcium levels increased significantly at 2 days after PCB (118) administration. Osteoclastic activation also occurred in the marker enzyme activities and mRNA expressions in vitro. Thus, we conclude that PCB (118) disrupts bone metabolism in goldfish both in vivo and in vitro experiments.     

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.