Evaluating legacy contaminants and emerging chemicals in marine environments using adverse outcome pathways and biological effects-directed analysis

Natural and synthetic chemicals are essential to our daily lives, food supplies, health care, industries and safe sanitation. At the same time protecting marine ecosystems and seafood resources from the adverse effects of chemical contaminants remains an important issue. Since the 1970s, monitoring of persistent, bioaccumulative and toxic (PBT) chemicals using analytical chemistry has provided important spatial and temporal trend data in three important contexts; relating to human health protection from seafood contamination, addressing threats to marine top predators and finally providing essential evidence to better protect the biodiversity of commercial and non-commercial marine species. A number of regional conventions have led to controls on certain PBT chemicals over several years (termed ‘legacy contaminants’; e.g. cadmium, lindane, polycyclic aromatic hydrocarbons [PAHs] and polychlorinated biphenyls [PCBs]). Analytical chemistry plays a key role in evaluating to what extent such regulatory steps have been effective in leading to reduced emissions of these legacy contaminants into marine environments. In parallel, the application of biomarkers (e.g. DNA adducts, CYP1A-EROD, vitellogenin) and bioassays integrated with analytical chemistry has strengthened the evidence base to support an ecosystem approach to manage marine pollution problems. In recent years, however, the increased sensitivity of analytical chemistry, toxicity alerts and wider environmental awareness has led to a focus on emerging chemical contaminants (defined as chemicals that have been detected in the environment, but which are currently not included in regulatory monitoring programmes and whose fate and biological impacts are poorly understood). It is also known that natural chemicals (e.g. algal biotoxins) may also pose a threat to marine species and seafood quality. Hence complex mixtures of legacy contaminants, emerging chemicals and natural biotoxins in marine ecosystems represent important scientific, economic and health challenges. In order to meet these challenges and pursue cost-effective scientific approaches that can provide evidence necessary to support policy needs (e.g. the European Marine Strategy Framework Directive), it is widely recognised that there is a need to (i) provide marine exposure assessments for priority contaminants using a range of validated models, passive samplers and biomarkers; (ii) integrate chemical monitoring data with biological effects data across spatial and temporal scales (including quality controls); and (iii) strengthen the evidence base to understand the relationship between exposure to complex chemical mixtures, biological and ecological impacts through integrated approaches and molecular data (e.g. genomics, proteomics and metabolomics). Additionally, we support the widely held view that (iv) that rather than increasing the analytical chemistry monitoring of large number of emerging contaminants, it will be important to target analytical chemistry towards key groups of chemicals of concern using effects-directed analysis. It is also important to evaluate to what extent existing biomarkers and bioassays can address various classes of emerging chemicals using the adverse outcome pathway (AOP) approach now being developed by the Organization for Economic Cooperation and Development (OECD) with respect to human toxicology and ecotoxicology.     

Exploring links between juvenile offenders and social disorganization at a large map scale: a Bayesian spatial modeling approach

This paper adopts a Bayesian spatial modeling approach to investigate the distribution of young offender residences in York Region, Southern Ontario, Canada, at the census dissemination area level. Few geographic researches have analyzed offender (as opposed to offense) data at a large map scale (i.e., using a relatively small areal unit of analysis) to minimize aggregation effects. Providing context is the social disorganization theory, which hypothesizes that areas with economic deprivation, high population turnover, and high ethnic heterogeneity exhibit social disorganization and are expected to facilitate higher instances of young offenders. Non-spatial and spatial Poisson models indicate that spatial methods are superior to non-spatial models with respect to model fit and that index of ethnic heterogeneity, residential mobility (1 year moving rate), and percentage of residents receiving government transfer payments are, respectively, the most significant explanatory variables related to young offender location. These findings provide overwhelming support for social disorganization theory as it applies to offender location in York Region, Ontario. Targeting areas where prevalence of young offenders could or could not be explained by social disorganization through decomposing the estimated risk map are helpful for dealing with juvenile offenders in the region. Results prompt discussion into geographically targeted police services and young offender placement pertaining to risk of recidivism. We discuss possible reasons for differences and similarities between the previous findings (that analyzed offense data and/or were conducted at a smaller map scale) and our findings, limitations of our study, and practical outcomes of this research from a law enforcement perspective.     

Social vulnerability assessment for mitigation of local earthquake risk in Los Angeles County

Comprehensive hazard mitigation involves (1) understanding natural systems, (2) assessment of interactions within and between social systems and the built environment, and (3) understanding geo-spatial processes. To achieve this, local emergency managers must recognize variability in vulnerable populations exposed to hazards and develop place-based emergency plans accordingly. In this study, we assess whether cities in Los Angeles County are subject to disproportionally greater earthquake losses modeled from a M7.8 earthquake on the San Andreas fault. Furthermore, we analyze whether the variation in demographic and socioeconomic characteristics across cities is associated with the earthquake losses. We were able to explain 23.2?% of variance in economic losses by looking at the percentage of minority residents, income, and renter residents in a city [F(3,84)?=?8.47; p?<?.001]. Cities with primarily minority residents had greater economic losses when compared to cities with primarily White residents (b?=?1.01; p?<?.001). When looking at the association between demographic predictors and potential casualty rate, the percentage of Hispanic residents was positively associated with the potential casualty rate. We argue that knowledge of the relationship between earthquake hazard and the demographic characteristics of people in the area at risk is essential to mitigate the local impact from earthquakes. In other words, we apply social vulnerability assessment as part of a comprehensive risk management framework to accelerate recovery after an event. Local policy makers and the private sector can use this approach to gain a better understanding of a city??s social vulnerability and adapt their preparedness efforts accordingly.     

Partial Migration Across Populations of White Perch (<Emphasis Type="Italic">Morone americana</Emphasis>): A Flexible Life History Strategy in a Variable Estuarine Environment

We evaluated the prevalence of partial migration, coexisting resident and migratory life history types, within six white perch (Morone americana) populations in sub-estuaries (Upper Bay, and Potomac, Choptank, Nanticoke, James, and York Rivers) of the Chesapeake Bay. Otolith stable isotope (δ¹⁸O) values were used to resolve fish habitat use along an estuarine salinity gradient and define resident or migratory behavior. The majority of adults within Upper Bay and Potomac River populations were resident, whereas individuals from the Choptank, Nanticoke, James, and York Rivers were predominantly migratory. Beyond population differences, large interannual variability in life history types was observed, likely due to differences in estuarine conditions that influence growth rate of individuals (e.g., temperature, zooplankton density). Because we observed partial migration in all study populations, we suggest that this trait is characteristic of this species, permitting plastic responses to variation in the estuarine environment.     

A climate-isotope regression model with seasonally-varying and time-integrated relationships

This study investigates multivariable and multiscalar climate-??¹⁸O relationships, through the use of statistical modeling and simulation. Three simulations, of increasing complexity, are used to generate time series of daily precipitation ??¹⁸O. The first simulation uses a simple local predictor (daily rainfall amount). The second simulation uses the same local predictor plus a larger-scale climate variable (a daily NAO index), and the third simulation uses the same local and non-local predictors, but with varying seasonal effect. Since these simulations all operate at the daily timescale, they can be used to investigate the climate-??¹⁸O patterns that arise at daily-interannual timescales. These simulations show that (1) complex links exist between climate-??¹⁸O relationships at different timescales, (2) the short-timescale relationships that underlie monthly predictor-??¹⁸O relationships can be recovered using only monthly ??¹⁸O and daily predictor variables, (3) a comparison between the simulations and observational data can elucidate the physical processes at work. The regression models developed are then applied to a 2-year dataset of monthly precipitation ??¹⁸O from Dublin and compared with event-scale data from the same site, which illustrates that the methodology works, and that the third regression model explains about 55% of the variance in ??¹⁸O at this site. The methodology introduced here can potentially be applied to historic monthly ??¹⁸O data, to better understand how multiple-integrated influences at short timescales give rise to climate-??¹⁸O patterns at monthly-interannual timescales.     

Polycyclic aromatic hydrocarbons in commercial fish and lobsters from the coastal waters of Madagascar following an oil spill in August 2009

Concentrations of polycyclic aromatic hydrocarbons were determined in species of commercial fish and lobsters following an oil-spill just off the protected Madagascan coastline. Samples were collected along the coastline within and outside the affected area. Summed PAH concentrations ranged from 1.9 μg kg⁻¹ to 63 μg kg⁻¹ wet weight, but with no higher molecular weight PAHs (>202 Da) being detected. All concentrations of benzo[a]pyrene, benz[a]anthracene and dibenz[a,h]anthracene were <0.1 μg kg⁻¹ wet weight, well within the EU and UK set limits for the protection of human health. Additionally, samples were calculated as the benzo[a]pyrene toxic equivalency quotient (TEQ) and found to be well below the level of concern in relation to health of human consumers. Evaluation of the biota PAH data indicated the origin of PAH was predominantly petrogenic with >80% arising from oil sources. Profile studies indicate a low-level multisource petrogenic contamination probably representing a pre-spill background for the area.     

The use of plastic debris as nesting material by a colonial seabird and associated entanglement mortality

Entanglement with plastic debris is a major cause of mortality in marine taxa, but the population-level consequences are unknown. Some seabirds collect marine debris for nesting material, which may lead to entanglement. Here we investigate the use of plastics as nesting material by northern gannets Morus bassanus and assess the associated levels of mortality. On average gannet nests contained 469.91 g (range 0-1293 g) of plastic, equating to an estimated colony total of 18.46 tonnes (range 4.47-42.34 tonnes). The majority of nesting material was synthetic rope, which appears to be used preferentially. On average 62.85 ± 26.84 (range minima 33-109) birds were entangled each year, totalling 525 individuals over eight years, the majority of which were nestlings. Although mortality rates are high, they are unlikely to have population-level effects. The use of synthetic fibres as nesting material is a common strategy among seabirds, but the impacts of entanglement warrants further investigation.     

The effect of methanogenesis on the geochemistry of low temperature water–Fe0–basalt reactions

Hydrogen gas produced in the subsurface from the hydration of mafic rocks is known to be a major energy source for chemolithotrophic life in extreme environments such as hydrothermal vents. The possibility that in situ anaerobic microorganisms present in the deep subsurface are sustained by low temperature H₂-generating water–rock reactions taking place around them is being investigated. Whether the growth and activity of H₂-utilizing microbes directly influences aqueous geochemistry, rates of mineral dissolution, and the chemical composition of the alteration products is also being quantitatively evaluated.To explore how microorganisms are affected by water–rock reactions, and how their activity may in turn affect reaction progress, laboratory experiments have been conducted to monitor the growth of a methanogenic Archaea in the presence of H_2(g) produced from low temperature water–Fe⁰–basalt reactions. In these systems, the conversion of Fe(II) to Fe(III) and subsequent hydrolysis of water is responsible for the production of H_2(g). To characterize key components of the geochemical system, time series measurements of H₂ and CH₄ gas concentrations, Fe and Si aqueous concentrations, and spatially resolved synchrotron-based analyses of microscale Fe distribution and speciation were conducted. Culture experiments were compared with an abiotic control to document changes in the geochemistry both in the presence and absence of the methanogen.In the control abiotic batch experiment, H₂ was continuously produced, until the headspace became saturated, while in the biotic experiments, microbial consumption of H₂ for methanogenesis draws H₂ down and produces CH₄. Purging the headspace gas reinitiates H₂ and CH₄ production in abiotic and culture experiments, respectively. Mass balance analysis of the amount of CH₄ produced suggests that the total H₂ production in microbial experiments does not exceed the abiotic experiment. Soluble Si concentrations, while buffered to relatively constant values, were higher in culture experiments than the abiotic control.Iron_(aq) concentrations appear to respond to perturbations of H₂ and CH₄ gas concentrations in both culture experiments and the abiotic control. A pulse of Fe preceded the rise in either H₂ or CH₄ production, and as the gas concentrations increased the Fe_(aq) decreased. Iron-bearing mineral assemblages change with increasing reaction time and mineral assemblages vary between culture experiments and the abiotic control. These geochemical trends suggest that there are different reaction paths between the culture experiments and the abiotic control.The hydration of mafic rocks is a common geologic reaction and one that has taken place on Earth for the majority of its history and is postulated to occur on Mars. These reactions are important because of their effect on the rheology and geochemistry of the ocean crust. While most often studied at temperatures of ～250 °C, this work suggests that at lower temperatures microorganisms may have a profound effect on what has long been thought to be solely an abiotic reaction, and may produce diagnostic mineral assemblages that will be preserved in the geological record.     

Particle fluxes in San Pedro Basin, California: A four-year record of sedimentation and physical forcing

Moored sediment traps were deployed from January 2004 through December 2007 at depths of 550 and 800 m in San Pedro Basin (SPB), CA (33°33.0′N, 118°26.5′W). Additionally, floating sediment traps were deployed at 100 and 200 m for periods of 12-24 h during spring 2005, fall 2007, and spring 2008. Average annual fluxes of mass, particulate organic carbon (POC), ??¹³C_org, particulate organic nitrogen (PON), ??¹⁵N-PON, biogenic silica (bSiO₂), calcium carbonate (CaCO₃), and detrital material (non-biogenic) were coupled with climate records and used to examine sedimentation patterns, vertical flux variability, and organic matter sources to this coastal region. Annual average flux values were determined by binning data by month and averaging the monthly averages. The average annual fluxes to 550 m were 516±42 mg/m² d for mass (sdom of the monthly averages, n=117), 3.18±0.26 mmol C/m² d for POC (n=111), 0.70±0.05 mmol/m² d for CaCO₃ (n=110), 1.31±0.21 mmol/m² d for bSiO₂ (n=115), and 0.35±0.03 mmol/m² d for PON (n=111). Fluxes to 800 and to 550 m were similar, within 10%. Annual average values of ??¹³C_org at 550 m were −21.8±0.2‰ (n=108), and ??¹⁵N averages were 8.9±0.2‰ (n=95). The timing of both high and low flux particle collection was synchronous between the two traps. Given the frequency of trap cup rotation (4-11 days), this argues for particle settling rates ≥83 m/d for both high and low flux periods. The moored traps were deployed over one of the wettest (2004-2005, 74.6 cm rainfall) and driest (2006-2007, 6.6 cm) rain years on record. There was poor correlation (Pearson's correlation coefficient, 95% confidence interval) of detrital mass flux with: C_org/N ratio (r=0.10, p=0.16); ??¹⁵N (r=−0.19, p=0.02); and rainfall (r=0.5, p=0.43), suggesting that runoff does not immediately cause increases in particle fluxes 15 km offshore. ??¹³C_org values suggest that most POC falling to the basin floor is marine derived. Coherence between satellite-derived chlorophyll a records from the trap location (±9 km² resolution) and SST data indicates that productivity and export occurs within a few days of upwelling and both of these parameters are reasonable predictors of POC export, with a time lag of a few days to 2 weeks (with no time lag—SeaWiFS chlorophyll a and POC flux, r=0.25, p=0.0014; chlorophyll a and bSiO₂ flux, r=0.28, p=0.0002).     

Polycyclic aromatic hydrocarbons in sediments,mussels and crustacea around a former gasworks site in Shoreham-by-Sea,UK

Concentrations of polycyclic aromatic hydrocarbons have been determined in sediments, mussels and crustacea in the vicinity of a former gasworks site by Shoreham Harbour, UK. Very high concentrations of PAH were found in the substrate, an ash-like material deposited on the former gasworks site, which exhibited a profile consistent with the major source of contamination being coal or coke tar produced during the period of gas production at the site. Elevated PAH concentrations were also found in mussels both from the beach below the former gasworks site, and from sites further to the east in Portslade and Hove. The significance of these concentrations were assessed using an approach which involved the calculation of benzo[a]pyrene equivalent conoentrations (BaPEs), summing concentrations of individual PAH on the basis of their comparative potency as carcinogens. BaPE ranged from values of, or close to, zero for crustacea, to 336 microg kg(-1) wet weight in mussels from Southwick Beach. The contaminated mussels are not exploited commercially but may be taken by casual gatherers, and notices have been posted to warn potential consumers.