Modeling the Emergence of Antibiotic Resistance in the Environment: an Analytical Solution for the Minimum Selection Concentration.

Environmental antibiotic risk management requires an understanding of how subinhibitory antibiotic concentrations contribute to the spread of resistance. We develop a simple model of competition between sensitive and resistant bacterial strains to predict the minimum selection concentration (MSC), the lowest level of antibiotic at which resistant bacteria are selected. We present an analytical solution for the MSC based on the routinely measured MIC, the selection coefficient (sc) that expresses fitness differences between strains, the intrinsic net growth rate, and the shape of the bacterial growth dose-response curve with antibiotic or metal exposure (the Hill coefficient [κ]). We calibrated the model by optimizing the Hill coefficient to fit previously reported experimental growth rate difference data. The model fit varied among nine compound-taxon combinations examined but predicted the experimentally observed MSC/MIC ratio well (R2 ≥ 0.95). The shape of the antibiotic response curve varied among compounds (0.7 ≤ κ ≤ 10.5), with the steepest curve being found for the aminoglycosides streptomycin and kanamycin. The model was sensitive to this antibiotic response curve shape and to the sc, indicating the importance of fitness differences between strains for determining the MSC. The MSC can be >1 order of magnitude lower than the MIC, typically by the factor scκ This study provides an initial quantitative depiction and a framework for a research agenda to examine the growing evidence of selection for resistant bacterial communities at low environmental antibiotic concentrations.

The association between community-associated Staphylococcus aureus colonization and disease: a meta-analysis.

BACKGROUND: Colonization with Staphylococcus aureus is a well-defined risk factor for disease in hospitals, which can range from minor skin infections to severe, systemic diseases. However, the generalizability of this finding has not been thoroughly investigated outside of the hospital environment. We aimed to assess the role of S. aureus colonization as a risk factor for disease in the community. METHODS: We performed a meta-analysis of observational studies and searched PubMed for articles published between December 1979 and May 23, 2016. We included cohort, cross-sectional, and case-control studies that reported quantitative estimates of both S. aureus colonization and disease statuses of all study subjects. We excluded studies on recently hospitalized subjects, long-term care facilities, surgery patients, dialysis patients, hospital staff, S. aureus outbreaks, and livestock-associated infections. Our meta-analysis was performed using random-effects analysis to obtain pooled odds ratios (ORs) to compare the odds of S. aureus disease with respect to S. aureus colonization status. RESULTS: We identified 3477 citations, of which 12 articles on 6998 subjects met the eligibility criteria. Overall, subjects colonized with S. aureus were more likely to progress to disease than those who were non-colonized: (OR 1.87, 95% CI 1.21-2.88, n = 7 studies). We observed a larger effect with methicillin-resistant S. aureus colonization (7.06, 4.60-10.84, n = 7 studies). However, the methicillin-sensitive S. aureus colonization was not associated with greater odds of disease (1.20, 0.69-2.06, n = 4 studies). Heterogeneity was present across studies in all of the subgroups: S. aureus (I2 = 95.0%, χ2 = 120.3, p < 0.001), MRSA (I2 = 92.8%, χ2 = 82.8, p = p < 0.001), and MSSA (I2 = 86.3%, χ2 = 21.8, p < 0.001). CONCLUSIONS: While the majority of papers individually support the assumption that colonization is a risk factor for S. aureus disease in the general population, there is marked heterogeneity between studies and further investigation is needed to identify the major sources of this variance. There is a shortage of literature addressing this topic in the community setting and a need for further research on colonization as a focus for disease prevention.

A multivariate analysis of CalEnviroScreen: comparing environmental and socioeconomic stressors versus chronic disease.

BACKGROUND: The health-risk assessment paradigm is shifting from single stressor evaluation towards cumulative assessments of multiple stressors. Recent efforts to develop broad-scale public health hazard datasets provide an opportunity to develop and evaluate multiple exposure hazards in combination. METHODS: We performed a multivariate study of the spatial relationship between 12 indicators of environmental hazard, 5 indicators of socioeconomic hardship, and 3 health outcomes. Indicators were obtained from CalEnviroScreen (version 3.0), a publicly available environmental justice screening tool developed by the State of California Environmental Protection Agency. The indicators were compared to the total rate of hospitalization for 14 ICD-9 disease categories (a measure of disease burden) at the zip code tabulation area population level. We performed principal component analysis to visualize and reduce the CalEnviroScreen data and spatial autoregression to evaluate associations with disease burden. RESULTS: CalEnviroScreen was strongly associated with the first principal component (PC) from a principal component analysis (PCA) of all 20 variables (Spearman ρ = 0.95). In a PCA of the 12 environmental variables, two PC axes explained 43% of variance, with the first axis indicating industrial activity and air pollution, and the second associated with ground-level ozone, drinking water contamination and PM2.5. Mass of pesticides used in agriculture was poorly or negatively correlated with all other environmental indicators, and with the CalEnviroScreen calculation method, suggesting a limited ability of the method to capture agricultural exposures. In a PCA of the 5 socioeconomic variables, the first PC explained 66% of variance, representing overall socioeconomic hardship. In simultaneous autoregressive models, the first environmental and socioeconomic PCs were both significantly associated with the disease burden measure, but more model variation was explained by the socioeconomic PCs. CONCLUSIONS: This study supports the use of CalEnviroScreen for its intended purpose of screening California regions for areas with high environmental exposure and population vulnerability. Study results further suggest a hypothesis that, compared to environmental pollutant exposure, socioeconomic status has greater impact on overall burden of disease.

Human exposure to methylmercury from crayfish (Procambarus clarkii) in China.

Methylmercury (MeHg) accumulation in aquatic food raises global concerns about human exposure to MeHg. Crayfish is the world's third largest farmed crustacean species and a favorite aquatic food in many countries. However, human health hazard due to MeHg exposure via crayfish consumption is unclear, partly because appropriate survey data are lacking. We report on mercury concentrations and speciation in edible tail muscle of crayfish collected from restaurants in 23 Chinese cities. On average, MeHg constituted 99.1 % of mercury in tail muscle, and MeHg concentrations were comparable with those reported for fish in China. Variation in MeHg concentrations was not attributable to broad geographic region (i.e., provinces) or tail length. For different populations, potential health risk (characterized by hazard quotient or HQ) of MeHg exposure through crayfish consumption depended largely on crayfish consumption rates. In particular, a health hazard (HQ > 1) was found for high-rate consumers (i.e., 95 %ile or higher) in some cities in the middle and lower reaches of the Yangtze River (MLYR), during the peak consumption season. Our results suggest that more attention should be paid to dietary MeHg intake via crayfish consumption in China, particularly for communities with high consumption in MLYR.

Nutrient supply and mercury dynamics in marine ecosystems: a conceptual model.

There is increasing interest and concern over the impacts of mercury (Hg) inputs to marine ecosystems. One of the challenges in assessing these effects is that the cycling and trophic transfer of Hg are strongly linked to other contaminants and disturbances. In addition to Hg, a major problem facing coastal waters is the impacts of elevated nutrient, particularly nitrogen (N), inputs. Increases in nutrient loading alter coastal ecosystems in ways that should change the transport, transformations and fate of Hg, including increases in fixation of organic carbon and deposition to sediments, decreases in the redox status of sediments and changes in fish habitat. In this paper we present a conceptual model which suggests that increases in loading of reactive N to marine ecosystems might alter Hg dynamics, decreasing bioavailabilty and trophic transfer. This conceptual model is most applicable to coastal waters, but may also be relevant to the pelagic ocean. We present information from case studies that both support and challenge this conceptual model, including marine observations across a nutrient gradient; results of a nutrient-trophic transfer Hg model for pelagic and coastal ecosystems; observations of Hg species, and nutrients from coastal sediments in the northeastern U.S.; and an analysis of fish Hg concentrations in estuaries under different nutrient loadings. These case studies suggest that changes in nutrient loading can impact Hg dynamics in coastal and open ocean ecosystems. Unfortunately none of the case studies is comprehensive; each only addresses a portion of the conceptual model and has limitations. Nevertheless, our conceptual model has important management implications. Many estuaries near developed areas are impaired due to elevated nutrient inputs. Widespread efforts are underway to control N loading and restore coastal ecosystem function. An unintended consequence of nutrient control measures could be to exacerbate problems associated with Hg contamination. Additional focused research and monitoring are needed to critically examine the link between nutrient supply and Hg contamination of marine waters.

Mercury isotopes link mercury in San Francisco Bay forage fish to surface sediments.

Identification of sources of biologically accessible Hg is necessary to fully evaluate Hg exposure in aquatic ecosystems. This study assesses the relationship between Hg in forage fish and Hg in surface sediments throughout San Francisco Bay (SF Bay) and evaluates processes influencing the incorporation of Hg into the aquatic food web. We measured the Hg stable isotope compositions of two nearshore fish species and compared them with previously reported analyses of colocated intertidal surface sediments. Fish δ(202)Hg values (mass-dependent fractionation) demonstrated a distinct spatial gradient within SF Bay that ranged from 0.60‰ in the south to -0.25‰ in the north. Fish δ(202)Hg values were consistently higher than sediment δ(202)Hg values by 0.73‰ (±0.16‰, 1SD). Fish and sediment δ(202)Hg values in SF Bay proper were well correlated (r(2) = 0.83), suggesting that sediment is a primary source of Hg to the nearshore aquatic food web. Fish Δ(199)Hg values (mass-independent fractionation) ranged from 0.46‰ to 1.55‰, did not correlate with sediment values, and yielded a Δ(199)Hg/Δ(201)Hg ratio of 1.26 (±0.01, 1SD; r(2) = 0.99). This mass-independent fractionation is consistent with photodegradation of MeHg to varying degrees at each site prior to incorporation into the food web.

Relative contribution of rice and fish consumption to bioaccessibility-corrected health risks for urban residents in eastern China.

There are global concerns about dietary exposure to metal(loid)s in foods. However, little is known about the relative contribution of rice versus fish to multiple metal(loid) exposure for the general population, especially in Asia where rice and fish are major food sources. We compared relative contributions of rice and fish consumption to multi-metal(loid) exposure on the city-scale (Nanjing) and province-scale in China. The effects of ingestion rate, metal(loid) level, and bioaccessibility were examined to calculate modeled risk from Cu, Zn, total As (TAs), inorganic As (iAs), Se, Cd, Pb, and methylmercury (MeHg). Metal(loid) levels in rice and fish samples collected from Nanjing City were generally low, except iAs. Metal(loid) bioaccessibilities in fish were higher than those in rice, except Se. Calculated carcinogenic risks induced by iAs intake (indicated by increased lifetime cancer risk, ILCR) were above the acceptable level (1 0 -4) in Nanjing City (median: 3 × 10-4 for female and 4 × 10-4 for male) and nine provinces (1.4 × 10-4 to 5.9 × 10-4) in China. Rice consumption accounted for 85.0% to 99.8% of carcinogenic risk. The non-carcinogenic hazard quotients (HQ) for single metals and hazard index (HI) for multi-metal exposure were < 1 in all cases, indicating of their slight non-carcinogen health effects associated. In Guangdong and Jiangsu provinces, results showed that rice and fish intake contributed similarly to the HI (i.e., 42.6% vs 57.4% in Guangdong and 54.6% vs 45.4% in Jiangsu). Sensitivity analysis indicated that carcinogenic risk was most sensitive to rice ingestion rate and rice iAs levels, while non-carcinogenic hazard (i.e., HQ and HI) was most sensitive to ingestion rate of fish and rice, and Cu concentration in rice. Our results suggest that rice is more important than fish for human dietary metal(loid) exposure risk in China, and carcinogenic risk from iAs exposure in rice requires particular attention.

Antimicrobial Drug-Resistant Gram-Negative Saprophytic Bacteria Isolated from Ambient, Near-Shore Sediments of an Urbanized Estuary: Absence of ß-Lactamase Drug-Resistance Genes.

We assessed the prevalence of antimicrobial resistance and screened for clinically relevant ß-lactamase resistance determinants in Gram-negative bacteria from a large urbanized estuary. In contrast to the broad literature documenting potentially hazardous resistance determinants near wastewater treatment discharge points and other local sources of aquatic pollution, we employed a probabilistic survey design to examine ambient, near-shore sediments. We plated environmental samples from 40 intertidal and shallow subtidal areas around San Francisco Bay (California, USA) on drug-supplemented MacConkey agar, and we tested isolates for antimicrobial resistance and presence of clinically relevant ß-lactamase resistance determinants. Of the 74 isolates identified, the most frequently recovered taxa were Vibrio spp. (40%), Shewanella spp. (36%), Pseudomonas spp. (11%), and Aeromonas spp. (4%). Of the 55 isolates tested for antimicrobial resistance, the Vibrio spp. showed the most notable resistance profiles. Most (96%) were resistant to ampicillin, and two isolates showed multidrug-resistant phenotypes: V. alginolyticus (cefotaxime, ampicillin, gentamicin, cefoxitin) and V. fluvialis (cefotaxime, ampicillin, cefoxitin). Targeted testing for class 1 integrons and presence of ß-lactam-resistance gene variants TEM, SHV, OXA, CTX-M, and Klebsiella pneumonia carbapenemase (KPC) did not reveal any isolates harboring these resistance determinants. Thus, while drug-resistant, Gram-negative bacteria were recovered from ambient sediments, neither clinically relevant strains nor mobile ß-lactam resistance determinants were found. This suggests that Gram-negative bacteria in this well-managed, urbanized estuary are unlikely to constitute a major human exposure hazard at this time.

High retention of silver sulfide nanoparticles in natural soils.

Silver, either in ionic or nanoparticulate form, is widely used in consumer products. However, silver sulfide (Ag2S) are more likely to be the form that Ag enters the environment. The retention of silver sulfide nanoparticles (Ag2S-NPs) in natural soils is critical for bioavailability and toxicity but remains unclear. Here, we examined the retention of Ag2S-NPs in 11 natural soils with varying properties using batch assays. More than 99% of Ag2S-NPs were retained in soil solids, irrespective of soil properties. Such high retention of Ag2S-NPs, at least partially, explained the distinct differences in phytoavailability performed in soil vs. liquid media in the literature. Nanoparticles containing Ag and S were identified in representative soil solids by high resolution transmission electron microscopy equipped with an energy dispersive X-ray spectrometer. Iron-rich acidic soil had a high dissolution of Ag2S-NPs ranging from 47.1% to 61.7% in porewater. In contrast to Ag2S-NPs, silver nanoparticles (AgNPs) and Ag+ in these soils were less retained (as described by Freundlich model) and the retention was closely associated with soil properties. These findings highlight the unique behaviors of Ag2S-NPs in natural soils.

Mercury in sport fish from the Sacramento-San Joaquin Delta region, California, USA.

Total mercury (Hg) concentrations were determined in fillet tissue of sport fish captured in the Sacramento-San Joaquin River Delta and surrounding tributaries, a region particularly impacted by historic gold and mercury mining activity. In 1999 and 2000, mercury concentrations were measured in 767 samples from ten fish species. Largemouth bass (Micropterus salmoides), the primary target species, exhibited a median Hg concentration of 0.53 mug g(-1) (N=406). Only 23 largemouth bass (6%) were below a 0.12 mug g(-1) threshold corresponding to a 4 meals per month safe consumption limit. Most of the largemouth bass (222 fish, or 55% of the sample) were above a 0.47 mug g(-1) threshold corresponding to a 1 meal per month consumption limit. Striped bass (Morone saxatilis), channel catfish (Ictalurus punctatus), white catfish (Ameirus catus), and Sacramento pikeminnow (Ptychocheilus grandis) also had relatively high concentrations, with 31% or more of samples above 0.47 mug g(-1). Concentrations were lowest in redear (Lepomis microlophus) and bluegill (Lepomis macrochirus) sunfish, with most samples below 0.12 mug g(-1), suggesting that targeting these species for sport and subsistence fishing may reduce human dietary exposure to Hg in the region. An improved method of analysis of covariance was performed to evaluate spatial variation in Hg in largemouth bass captured in 2000, while accounting for variability in fish length. Using this approach, Hg concentrations were significantly elevated in the Feather River, northern Delta, lower Cosumnes River, and San Joaquin River regions. In spite of elevated Hg concentrations on all of its tributaries, the central Delta had concentrations that were low both in comparison to safe consumption guidelines and to other locations.

Assessment of potential aquatic herbicide impacts to California aquatic ecosystems.

A series of legal decisions culminated in 2002 with the California State Water Resources Control Board funding the San Francisco Estuary Institute to develop and implement a 3-year monitoring program to determine the potential environmental impacts of aquatic herbicide applications. The monitoring program was intended to investigate the behavior of all aquatic pesticides in use in California, to determine potential impacts in a wide range of water-body types receiving applications, and to help regulators determine where to direct future resources. A tiered monitoring approach was developed to achieve a balance between program goals and what was practically achievable within the project time and budget constraints. Water, sediment, and biota were collected under "worst-case" scenarios in close association with herbicide applications. Applications of acrolein, copper sulfate, chelated copper, diquat dibromide, glyphosate, fluridone, triclopyr, and 2,4-D were monitored. A range of chemical analyses, toxicity tests, and bioassessments were conducted. At each site, risk quotients were calculated to determine potential impacts. For sediment-partitioning herbicides, sediment quality triad analysis was performed. Worst-case scenario monitoring and special studies showed limited short-term and no long-term toxicity directly attributable to aquatic herbicide applications. Risk quotient calculations called for additional risk characterizations; these included limited assessments for glyphosate and fluridone and more extensive risk assessments for diquat dibromide, chelated copper products, and copper sulfate. Use of surfactants in conjunction with aquatic herbicides was positively associated with greater ecosystem impacts. Results therefore warrant full risk characterization for all adjuvant compounds.

Contaminant concentrations and histopathological effects in Sacramento splittail (Pogonichthys macrolepidotus).

Sacramento splittail (Pogonichthys macrolepidotus) is a species of special concern in California, due to multiple anthropogenic stressors. To better understand the potential impact of contaminant exposure, adult splittail were captured from the Sacramento-San Joaquin River Delta (California, USA) and analyzed for histopathology and contaminant exposure. Organochlorine contaminants (PCBs, DDTs, dieldrin, chlordanes, and PBDEs) and trace metals (Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Se, Sn, V, and Zn) were detected in the tissues of all fish. In many samples, human health screening values were exceeded for PCBs (83 of 90 samples), DDTs (32 samples), and dieldrin (37 samples). In contrast, thresholds for fish effects were rarely exceeded. Histopathological analysis indicated the presence of macrophage aggregates in gonads, kidneys, and liver and a high incidence of liver abnormalities. In the liver, observed effects were often moderate to severe for glycogen depletion (55 of 95 fish), lipidosis (hepatocellular vacuolation; 51 fish), and cytoplasmic inclusion bodies (33 fish). Correlations between histopathology and tissue contaminant concentrations were weak and inconsistent. Significant correlations were observed between histopathology indicators and reductions in fish size, body condition, lipid content, and liver weight. These results suggest that splittail histopathology varies as a function of health and nutritional status, rather than exposure to legacy organic and metal pollutants.

Bioaccessibility-corrected risk assessment of urban dietary methylmercury exposure via fish and rice consumption in China.

The role of seafood consumption for dietary methylmercury (MeHg) exposure is well established. Recent studies also reveal that rice consumption can be an important pathway for dietary MeHg exposure in some Hg-contaminated areas. However, little is known about the relative importance of rice versus finfish in MeHg exposure for urban residents in uncontaminated areas. Especially, the lack of data on MeHg bioaccessibility in rice hinders accurately assessing MeHg exposure via rice consumption, and its importance compared to fish. By correcting commonly used risk models with quantified MeHg bioaccessibility, we provide the first bioaccessibility-corrected comparison on MeHg risk in rice and fish for consumers in non-contaminated urban areas of China, on both city- and province-scales. Market-available fish and rice samples were cooked and quantified for MeHg bioaccessibility. Methylmercury bioaccessibility in rice (40.5±9.4%) was significantly (p<0.05) lower than in fish (61.4±14.2%). This difference does not result from selenium content but may result from differences in protein or fiber content. Bioaccessibility-corrected hazard quotients (HQs) were calculated to evaluate consumption hazard of MeHg for consumers in Nanjing city, and Monte Carlo Simulations were employed to evaluate uncertainty and variability. Results indicate that MeHg HQs were 0.14 (P50) and 0.54 (P90). Rice consumption comprised 27.2% of the overall dietary exposure to MeHg in Nanjing, while fish comprised 72.8%. Employing our bioaccessibility data combined with literature parameters, calculated relative contribution to MeHg exposure from rice (versus fish) was high in western provinces of China, including Sichuan (95.6%) and Guizhou (81.5%), and low to moderate in eastern and southern provinces (Guangdong: 6.6%, Jiangsu: 17.7%, Shanghai: 15.1%, Guangxi: 20.6%, Jiangxi: 22.8% and Hunan: 25.9%). This bioaccessibility-corrected comparison of rice versus fish indicates that rice consumption can substantively contribute to dietary MeHg exposure risk for urban populations in Asia, and should be regularly included in dietary MeHg exposure assessment.

Mechanistic understanding of low methylmercury bioaccessibility from crayfish (Procambarus clarkii) muscle tissue.

Recent research indicates that dietary exposure to mercury and other metals from crayfish consumption poses a human health concern, particularly in regions with high crayfish-consuming populations. To better understand consumption risk from methylmercury (MeHg), we quantified MeHg bioaccessibility in edible tail muscle of cooked red swamp crayfish (Procambarus clarkii, collected from seven cities in China), versus cooked fillet tissue of two finfish species: yellow croaker (Larimichthys polyactis) and snakehead (Channa argus). Results indicated that digestive solubilization rate (DSR) of MeHg in crayfish (7.8±3.9% for restaurant-crayfish and 9.8±0.8% for market-crayfish) was lower than the rate in yellow croaker (25.8±2.7%) and snakehead (26.2±4.7%) tissue, suggesting that relatively low MeHg bioaccessibility in crayfish may reduce dietary exposure to humans. Three possible mechanisms for the reduced MeHg DSR in crayfish tissue were examined: MeHg-Se interactions, MeHg subcellular fractionation, and Hg-amino acid binding. Selenium concentrations were comparable among the examined species, and no significant relationship was observed between tissue Se and MeHg DSR. Similarly, observed differences in subcellular fractionation of MeHg could not explain the species-specific MeHg DSR. Therefore, MeHg-Se interactions and MeHg subcellular fractionation do not explain the relatively low MeHg bioaccessibility in crayfish. Significantly higher cysteine and arginine content was found in crayfish than in the finfish. We suspect that the lower MeHg bioaccessibility of crayfish tail muscle may be attributed to the higher cysteine concentrations, and thus, stronger MeHg-protein binding in crayfish. These results support the interpretation that bioaccessibility differences will alter risk interpretations for MeHg, especially when comparing hazard across aquatic food types.

Long-term variation in concentrations and mass loads in a semi-arid watershed influenced by historic mercury mining and urban pollutant sources.

Urban watersheds are significantly anthropogenically-altered landscapes. Most previous studies cover relatively short periods, without addressing concentrations, loads, and yields in relation to annual climate fluctuations, and datasets on Ag, Se, PBDEs, and PCDD/Fs are rare. Intensive storm-focused sampling and continuous turbidity monitoring were employed to quantify pollution at two locations in the Guadalupe River (California, USA). At a downstream location, we determined loads of suspended sediment (SS) for 14yrs., mercury (HgT), PCBs, and total organic carbon (TOC) (8yrs), total methylmercury (MeHgT) (6yrs), nutrients, and trace elements including Ag and Se (3yrs), DDTs, chlordanes, dieldrin, and PBDEs (2yrs), and PCDD/Fs (1yr). At an upstream location, we determined loads of SS for 4yrs. and HgT, MeHgT, PCBs and PCDD/Fs for 1yr. These data were compared to previous studies, climatically adjusted, and used to critically assess the use of small datasets for estimating annual average conditions. Concentrations and yields in the Guadalupe River appear to be atypical for total phosphorus, DDTs, dieldrin, HgT, MeHgT, Cr, Ni, and possibly Se due to local conditions. Other pollutants appear to be similar to other urban systems. On average, wet season flow varied by 6.5-fold and flow-weighted mean (FWM) concentrations varied 4.4-fold, with an average 7.1-fold difference between minimum and maximum annual loads. Loads for an average runoff year for each pollutant were usually less than the best estimate of long-term average. The arithmetic average of multiple years of load data or a FWM concentration combined with mean annual flow was also usually below the best estimate of long-term average load. Mean annual loads using sampled years were also less than the best estimate of long-term average by a mean of 2.2-fold. Climatic adjustment techniques are needed for computing estimates of long-term average annual loads.

Decline in methylmercury in museum-preserved bivalves from San Francisco Bay, California.

There are ongoing efforts to manage mercury and nutrient pollution in San Francisco Bay (California, USA), but historical data on biological responses are limited. We used bivalves preserved in formalin or ethanol from museum collections to investigate long-term trends in methylmercury (MeHg) concentrations and carbon and nitrogen isotopic signatures. In the southern reach of the estuary, South Bay, MeHg in the Asian date mussel (Musculista senhousia) significantly declined over the study duration (1970 to 2012). Mean MeHg concentrations were highest (218ng/g dry weight, dw) in 1975 and declined 3.8-fold (to 57ng/g dw) by 2012. This decrease corresponded with closure of the New Almaden Mercury Mines and was consistent with previously observed declines in sediment core mercury concentrations. In contrast, across all sites, MeHg in the overbite clam (Potamocorbula amurensis) increased 1.3-fold from 64ng/g dw before 2000 to 81ng/g dw during the 2000s and was higher than in M. senhousia. Pearson correlation coefficients of the association between MeHg and δ13C or δ15N provided no evidence that food web alterations explained changing MeHg concentrations. However, isotopic composition shifted temporally. South Bay bivalve δ15N increased from 12‰ in the 1970s to 18‰ in 2012. This increase corresponded with increasing nitrogen loadings from wastewater treatment plants until the late 1980s and increasing phytoplankton biomass from the 1990s to 2012. Similarly, a 3‰ decline in δ13C from 2002 to 2012 may represent greater utilization of planktonic food sources. In a complimentary 90day laboratory study to validate use of these preserved specimens, preservation had only minor effects (<0.5‰) on δ13C and δ15N. MeHg increased following preservation but then stabilized. These are the first documented long-term trends in biota MeHg and stable isotopes in this heavily impacted estuary and support the utility of preserved specimens to infer contaminant and biogeochemical trends.

Are Chinese consumers at risk due to exposure to metals in crayfish? A bioaccessibility-adjusted probabilistic risk assessment.

Freshwater crayfish, the world's third largest crustacean species, has been reported to accumulate high levels of metals, while the current knowledge of potential risk associated with crayfish consumption lags behind that of finfish. We provide the first estimate of human health risk associated with crayfish (Procambarus clarkii) consumption in China, the world's largest producer and consumer of crayfish. We performed Monte Carlo Simulation on a standard risk model parameterized with local data on metal concentrations, bioaccessibility (φ), crayfish consumption rate, and consumer body mass. Bioaccessibility of metals in crayfish was found to be variable (68-95%) and metal-specific, suggesting a potential influence of metal bioaccessibility on effective metal intake. However, sensitivity analysis suggested risk of metals via crayfish consumption was predominantly explained by consumption rate (explaining >92% of total risk estimate variability), rather than metals concentration, bioaccessibility, or body mass. Mean metal concentrations (As, Cd, Cu, Ni, Pb, Se and Zn) in surveyed crayfish samples from 12 provinces in China conformed to national safety standards. However, risk calculation of φ-modified hazard quotient (HQ) and hazard index (HI) suggested that crayfish metals may pose a health risk for very high rate consumers, with a HI of over 24 for the highest rate consumers. Additionally, the φ-modified increased lifetime risk (ILTR) for carcinogenic effects due to the presence of As was above the acceptable level (10(-5)) for both the median (ILTR=2.5×10(-5)) and 90th percentile (ILTR=1.8×10(-4)), highlighting the relatively high risk of As in crayfish. Our results suggest a need to consider crayfish when assessing human dietary exposure to metals and associated health risks, especially for high crayfish-consuming populations, such as in China, USA and Sweden.

Seasonal, interannual, and long-term variation in sport fish contamination, San Francisco Bay.

This study documents changes in contamination over time at seasonal, interannual, and decadal time scales for sport fish collected in San Francisco Bay. Samples from seven fish species were prepared according to common consumption practices (muscle fillets either with or without skin) and analyzed for trace metals (mercury and selenium) and trace organochlorine contaminants (PCBs, DDTs, chlordanes, and dieldrin). In 2000, sport fish samples exceeded human health screening values for mercury, PCBs, DDTs, selenium, and dieldrin but did not exceed screening values for chlordanes. On a seasonal time scale, white croaker (Genyonemus lineatus) exhibited significantly lower PCB and lipid concentrations in spring, and a general increase in concentrations in other seasons. When monitoring data were compared among 1994, 1997, and 2000, analysis of variance indicated that concentrations of mercury, PCBs, DDTs, and chlordanes varied significantly among years for several fish species. Interannual variation in DDTs often correlated to changes in sampled fish size or lipid content among years. Interannual variation in mercury and PCBs was evident in striped bass (Morone saxatilis) but absent in shiner surfperch (Cymatogaster aggregata), leopard shark (Triakis semifasciata), and white croaker. The higher interannual variability of striped bass contaminant concentrations may result from migratory behavior and wide home ranges. Chlordanes significantly declined between 1994 and 2000 in white croaker and striped bass. Of the historical data analyzed (1986-2000), only DDT concentrations in white sturgeon (Acipenser transmontanus) showed evidence of a significant decline. Neither PCBs nor selenium showed evidence of a trend in white sturgeon. Between 1970 and 2000, mercury concentrations in striped bass showed no evidence of a trend. The absence of recent trends in mercury may result from the presence of widespread and historic sources, with use reductions occurring in the early 20th century. In contrast to mercury, apparent recent declines in fish tissue DDT and chlordane concentrations may result from use curtailment in the 1970s and 1980s.

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)).

A tiered assessment framework to evaluate human health risk of contaminated sediment.

For sediment contaminated with bioaccumulative pollutants (e.g., PCBs and organochorine pesticides), human consumption of seafood that contain bioaccumulated sediment-derived contaminants is a well-established exposure pathway. Historically, regulation and management of this bioaccumulation pathway has focused on site-specific risk assessment. The state of California (United States) is supporting the development of a consistent and quantitative sediment assessment framework to aid in interpreting a narrative objective to protect human health. The conceptual basis of this framework focuses on 2 key questions: 1) do observed pollutant concentrations in seafood from a given site pose unacceptable health risks to human consumers? and 2) is sediment contamination at a site a significant contributor to seafood contamination? The first question is evaluated by interpreting seafood tissue concentrations at the site, based on health risk calculations. The second question is evaluated by interpreting site-specific sediment chemistry data using a food web bioaccumulation model. The assessment framework includes 3 tiers (screening assessment, site assessment, and refined site assessment), which enables the assessment to match variations in data availability, site complexity, and study objectives. The second and third tiers use a stochastic simulation approach, incorporating information on variability and uncertainty of key parameters, such as seafood contaminant concentration and consumption rate by humans. The framework incorporates site-specific values for sensitive parameters and statewide values for difficult to obtain or less sensitive parameters. The proposed approach advances risk assessment policy by incorporating local data into a consistent region-wide problem formulation, applying best available science in a streamlined fashion.