Measuring and monitoring persistent organic pollutants in the context of risk assessment

Due to growing concerns regarding persistent organic pollutants (POPs) in the environment, extensive studies and monitoring programs have been carried out in the last two decades to determine their concentrations in water, sediment, and more recently, in biota. An extensive review and analysis of the existing literature shows that whilst the vast majority of these efforts either attempt to compare (a) spatial changes (to identify "hot spots"), or (b) temporal changes to detect deterioration/improvement occurring in the environment, most studies could not provide sufficient statistical power to estimate concentrations of POPs in the environment and detect spatial and temporal changes. Despite various national POPs standards having been established, there has been a surprising paucity of emphasis in establishing accurate threshold concentrations that indicate potential significant threats to ecosystems and public health. Although most monitoring programs attempt to check compliance through reference to certain "environmental quality objectives", it should be pointed out that many of these established standards are typically associated with a large degree of uncertainty and rely on a large number of assumptions, some of which may be arbitrary. Non-compliance should trigger concern, so that the problem can be tracked down and rectified, but non-compliance must not be interpreted in a simplistic and mechanical way. Contaminants occurring in the physical environment may not necessarily be biologically available, and even when they are bioavailable, they may not necessarily elicit adverse biological effects at the individual or population levels. As such, we here argue that routine monitoring and reporting of abiotic and biotic POPs concentrations could be of limited use, unless such data can be related directly to the assessment of public health and ecological risks. Risk can be inferred from the ratio of predicted environmental concentration (PEC) and the predicted no effect concentration (PNEC). Currently, the paucity of data does not allow accurate estimation of PNEC, and future endeavors should therefore, be devoted to determine the threshold concentrations of POPs that can cause undesirable biological effects on sensitive receivers and important biological components in the receiving environment (e.g. keystone species, populations with high energy flow values, etc.), to enable derivation of PNECs based on solid scientific evidence and reduce uncertainty. Using the threshold body burden of POPs required to elicit damages of lysosomal integrity in the green mussel (Perna virvidis) as an example, we illustrate how measurement of POPs in body tissue could be used in predicting environmental risk in a meaningful way.     

Antioxidant responses to polycyclic aromatic hydrocarbons and organochlorine pesticides in green-lipped mussels (Perna viridis): do mussels "integrate" biomarker responses?

Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCs) are generally present in the marine environment in complex mixtures. The ecotoxicological nature of contaminant interactions, however, is poorly understood, with most scientific observations derived from single contaminant exposure experiments. The objective of this experiment was to examine dose-response relationships between antioxidant parameters and body contaminant levels in mussels exposed to different exposure regimes under laboratory conditions. Accordingly, the green-lipped mussel, Perna viridis, was challenged with a mixture of PAHs (anthracene, fluoranthene, pyrene, benzo[a]pyrene) and OC pesticides (alpha-HCH, aldrin, dieldrin, p,p'-DDT) over a 4 week period. Contaminants were delivered under four different dosing regimes, with all treatments receiving the same total contaminant load by the end of the exposure period. Antioxidant biomarkers were measured after 1, 2, 3 and 4 weeks, including glutathione (GSH), gluathione-S-transferase (GST), superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), glutathione reductase (GR) and lipid peroxidase (LPO). GST and CAT were induced in hepatic tissues in most of the exposure regimes, with the majority of significant induction occurring in a constant exposure regime and a two-step alternate exposure regime. Significant differences among exposure regimes were detected in the body burden of contaminants after 28 days. Hepatic CAT and GSH are proposed as potentially useful biomarkers as they showed good correlation with target contaminants and were not readily affected by different dosing patterns.     

Antioxidant responses to polycyclic aromatic hydrocarbons and organochlorine pesticides in green-lipped mussels (Perna viridis): Do mussels “integrate” biomarker responses?

Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCs) are generally present in the marine environment in complex mixtures. The ecotoxicological nature of contaminant interactions, however, is poorly understood, with most scientific observations derived from single contaminant exposure experiments. The objective of this experiment was to examine dose-response relationships between antioxidant parameters and body contaminant levels in mussels exposed to different exposure regimes under laboratory conditions. Accordingly, the green-lipped mussel, Perna viridis, was challenged with a mixture of PAHs (anthracene, fluoranthene, pyrene, benzo[a]pyrene) and OC pesticides (α-HCH, aldrin, dieldrin, p,p′-DDT) over a 4 week period. Contaminants were delivered under four different dosing regimes, with all treatments receiving the same total contaminant load by the end of the exposure period. Antioxidant biomarkers were measured after 1, 2, 3 and 4 weeks, including glutathione (GSH), gluathione-S-transferase (GST), superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), glutathione reductase (GR) and lipid peroxidase (LPO). GST and CAT were induced in hepatic tissues in most of the exposure regimes, with the majority of significant induction occurring in a constant exposure regime and a two-step alternate exposure regime. Significant differences among exposure regimes were detected in the body burden of contaminants after 28 days. Hepatic CAT and GSH are proposed as potentially useful biomarkers as they showed good correlation with target contaminants and were not readily affected by different dosing patterns.     

Resolving the contributing factors to Mississippi Delta subsidence: Past and Present

To date, quantification of individual components that contribute to shallow and deep‐seated subsidence in passive margin deltas worldwide has proven problematic. A new, regional gridded chronostratigraphic dataset for the Lower Mississippi Delta region, derived from 80,928 well reports across the northern Gulf of Mexico (GOM), has bridged the disparity between geodetic mean rates measuring total land surface subsidence across annual‐to‐decadal timescales and the deep‐seated stratigraphic subsidence rates that record isostatic response over timescales of >10⁴ years. Through a quantitative assessment of gridded chronostratigraphic surfaces, sections, and subsidence rates extending from the Middle Pleistocene (0.58 Ma) to the Late Pliocene (3.85 Ma), we identify both temporal and spatial variability in deep‐seated subsidence across the northern GOM. Targeted deep‐seated subsidence data extracted across prior GOM Holocene sea‐level sample locations have revealed more than an order of magnitude greater rates of isostatic compensation in the Mississippi depocentre versus similar GOM sea‐level control sites in Florida and Alabama, casting doubt on efforts towards a representative Holocene sea‐level curve. Spatial variability in subsidence was also assessed locally in both the strike and dip directions to assess the contributions of growth faults. Fault throw displacement magnitude was discovered to decrease with depth, accounting for less than half of the total deep‐seated subsidence record of the Middle Pleistocene. Temporal subsidence complexities were also revealed including a direct, inverse logarithmic relationship between subsidence rate and time indicating variable subsidence component controls across different timescales. Despite the spatial and temporal complexities, this dataset serves as the first regional baseline for deep‐seated subsidence rates across the northern GOM.     

Effects of hull–ice friction coefficient on predictions of pack ice forces for moored offshore vessels

Designers and offshore operators frequently predict pack ice loading on offshore vessels by conducting scale model tests. One factor that can affect pack ice loading is the hull–ice friction coefficient. This research investigates the effect of hull–ice friction coefficients for a moored offshore vessel model and includes ice floe size and ice concentration as additional variables. A method of non-dimensional analysis is modified in order to deal with the multivariate nature of the new data. The resulting non-dimensional equation provides insight on relationships between the predicted pack ice force and the variables under investigation. The relationship between pack ice force and hull–ice friction coefficient is shown to be approximately a fourth root function, while the relationship for ice floe size, non-dimensionalised by the vessel beam, is approximately linear. The relationship between predicted pack ice force and ice concentration exists in a band bounded by cubic and sixth power curves. Applying the modified equation to the previous data sets shows the current analysis slightly improves the normalization of pack ice forces.     

Compositional changes in natural gas bubble plumes: observations from the Coal Oil Point marine hydrocarbon seep field

Detailed measurements of bubble composition, dissolved gas concentrations, and plume dynamics were conducted during a 9-month period at a very intense, shallow (22-m water depth) marine hydrocarbon seep in the Santa Barbara Channel, California. Methane, carbon dioxide, and heavier hydrocarbons were lost from rising seep bubbles, while nitrogen and oxygen were gained. Within the rising seawater bubble plume, dissolved methane concentrations were more than 4 orders of magnitude greater than atmospheric equilibrium concentrations. Strong upwelling flows were observed and bubble-rise times were ~40 s, demonstrating the rapid exchange of gases within the bubble plume.     

Dynamic response of a tanker moored to an articulated loading platform

An analytical model was developed for the dynamic analysis of an articulated loading platform in an operation condition, while remaining in a head seas position. The environmental excitation considered, resulting from groups of regular waves, included first- and second-order force contributions. The nylon hawser connecting the tanker to the ALP was modeled as a nonlinear spring. The hydrodynamic load on the tower was evaluated using Morison's equation, which was modified to account for the relative motion of the tower and the fluid particles. The hydrodynamic load on the tanker was calculated using linear diffraction theory based on the 2-D Helmholtz equation. The “near field” approach of Pinkster was used to evaluate the drift force.     

How processing digital elevation models can affect simulated water budgets

For regional models, the shallow water table surface is often used as a source/sink boundary condition, as model grid scale precludes simulation of the water table aquifer. This approach is appropriate when the water table surface is relatively stationary. Since water table surface maps are not readily available, the elevation of the water table used in model cells is estimated via a two-step process. First, a regression equation is developed using existing land and water table elevations from wells in the area. This equation is then used to predict the water table surface for each model cell using land surface elevation available from digital elevation models (DEM). Two methods of processing DEM for estimating the land surface for each cell are commonly used (value nearest the cell centroid or mean value in the cell). This article demonstrates how these two methods of DEM processing can affect the simulated water budget. For the example presented, approximately 20% more total flow through the aquifer system is simulated if the centroid value rather than the mean value is used. This is due to the one-third greater average ground water gradients associated with the centroid value than the mean value. The results will vary depending on the particular model area topography and cell size. The use of the mean DEM value in each model cell will result in a more conservative water budget and is more appropriate because the model cell water table value should be representative of the entire cell area, not the centroid of the model cell.     

Equifinality of formal (DREAM) and informal (GLUE) Bayesian approaches in hydrologic modeling?

In recent years, a strong debate has emerged in the hydrologic literature regarding what constitutes an appropriate framework for uncertainty estimation. Particularly, there is strong disagreement whether an uncertainty framework should have its roots within a proper statistical (Bayesian) context, or whether such a framework should be based on a different philosophy and implement informal measures and weaker inference to summarize parameter and predictive distributions. In this paper, we compare a formal Bayesian approach using Markov Chain Monte Carlo (MCMC) with generalized likelihood uncertainty estimation (GLUE) for assessing uncertainty in conceptual watershed modeling. Our formal Bayesian approach is implemented using the recently developed differential evolution adaptive metropolis (DREAM) MCMC scheme with a likelihood function that explicitly considers model structural, input and parameter uncertainty. Our results demonstrate that DREAM and GLUE can generate very similar estimates of total streamflow uncertainty. This suggests that formal and informal Bayesian approaches have more common ground than the hydrologic literature and ongoing debate might suggest. The main advantage of formal approaches is, however, that they attempt to disentangle the effect of forcing, parameter and model structural error on total predictive uncertainty. This is key to improving hydrologic theory and to better understand and predict the flow of water through catchments.