Sediment-associated aliphatic and aromatic hydrocarbons in coastal British Columbia, Canada: concentrations, composition, and associated risks to protected sea otters

Sediment-associated hydrocarbons can pose a risk to wildlife that rely on benthic marine food webs. We measured hydrocarbons in sediments from the habitat of protected sea otters in coastal British Columbia, Canada. Alkane concentrations were dominated by higher odd-chain n-alkanes at all sites, indicating terrestrial plant inputs. While remote sites were dominated by petrogenic polycyclic aromatic hydrocarbons (PAHs), small harbour sites within sea otter habitat and sites from an urban reference area reflected weathered petroleum and biomass and fossil fuel combustion. The partitioning of hydrocarbons between sediments and adjacent food webs provides an important exposure route for sea otters, as they consume ∼25% of their body weight per day in benthic invertebrates. Thus, exceedences of PAH sediment quality guidelines designed to protect aquatic biota at 20% of the sites in sea otter habitat suggest that sea otters are vulnerable to hydrocarbon contamination even in the absence of catastrophic oil spills.     

The Anthropocene: From Global Change to Planetary Stewardship

Over the past century, the total material wealth of humanity has been enhanced. However, in the twenty-first century, we face scarcity in critical resources, the degradation of ecosystem services, and the erosion of the planet's capability to absorb our wastes. Equity issues remain stubbornly difficult to solve. This situation is novel in its speed, its global scale and its threat to the resilience of the Earth System. The advent of the Anthropence, the time interval in which human activities now rival global geophysical processes, suggests that we need to fundamentally alter our relationship with the planet we inhabit. Many approaches could be adopted, ranging from geoengineering solutions that purposefully manipulate parts of the Earth System to becoming active stewards of our own life support system. The Anthropocene is a reminder that the Holocene, during which complex human societies have developed, has been a stable, accommodating environment and is the only state of the Earth System that we know for sure can support contemporary society. The need to achieve effective planetary stewardship is urgent. As we go further into the Anthropocene, we risk driving the Earth System onto a trajectory toward more hostile states from which we cannot easily return.     

Contaminant Exposure of Barn Swallows Nesting on Bayou D'Inde, Calcasieu Estuary, Louisiana, USA

Current and historical point source discharges, storm water runoff, and accidental spills have contaminated the water, sediment, and biota within the Calcasieu Estuary in southwestern Louisiana. In 2003, barn swallow (Hirundo rustica) eggs and nestlings were collected beneath two bridges that cross Bayou d′Inde, the most contaminated waterway within the Calcasieu Estuary. Samples were also collected from a bridge over Bayou Teche, a reference site in south central Louisiana. Polychlorinated biphenyl (PCB) concentrations in barn swallow eggs and nestlings were significantly higher at the downstream site on Bayou d′Inde (2.8 μ g/g PCBs in eggs and 1.5 μ g/g PCBs in nestlings) than at the other two sites (< 0.2 μ g/g PCBs in eggs and nestlings at both sites). Ethoxyresorufin-O-dealkylase activity in nestling livers was significantly higher at the downstream site on Bayou d′Inde (50 pmol/min/mg) compared to the other two locations (24 pmol/min/mg, each), probably because of exposure to PCBs. Polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran concentrations in eggs and polycyclic aromatic hydrocarbons in nestlings were at background concentrations at all sites. Trace element concentrations in barn swallow eggs and nestling livers were at background levels and did not differ among the three sites. A biomarker of DNA damage did not differ among sites.     

Spatial Relationships Between Water Quality and Pesticide Application Rates in Agricultural Watersheds

Pesticide applications to agricultural lands in California, USA, are reported to a central data base, while data on water and sediment quality are collected by a number of monitoring programs. Data from both sources are geo-referenced, allowing spatial analysis of relationships between pesticide application rates and the chemical and biological condition of water bodies. This study collected data from 12 watersheds, selected to represent a range of pesticide usage. Water quality parameters were measured during six surveys of stream sites receiving runoff from the selected watershed areas. This study had three objectives: to evaluate the usefulness of pesticide application data in selecting regional monitoring sites, to provide information for generating and testing hypotheses about pesticide fate and effects, and to determine whether in-stream nitrate concentration was a useful surrogate indicator for regional monitoring of toxic substances. Significant correlations were observed between pesticide application rates and in-stream pesticide concentrations (p < 0.05) and toxicity (p < 0.10). In-stream nitrate concentrations were not significantly correlated with either the amount of pesticides applied, in-stream pesticide concentrations, or in-stream toxicity (all p > 0.30). Neither total watershed area nor the area in which pesticide usage was reported correlated significantly with the amount of pesticides applied, in-stream pesticide concentrations, or in-stream toxicity (all p > 0.14). In-stream pesticide concentrations and effects were more closely related to the intensity of pesticide use than to the area under cultivation.     

Evaluation of short-term Ogawa passive, photolytic, and federal reference method sampling devices for nitrogen oxides in El Paso and Houston, Texas

Passive Sampling Devices (PSDs) have been successfully used by government and academic agencies to monitor common ambient air pollutants such as ozone and nitrogen dioxide (NO(2)). Most PSD studies have involved long-term (e.g. bi-weekly or monthly) sampling. But the Passive Ozone Network of Dallas (POND) studies of 1998 and 1999 showed that high quality 24-hour and 12-hour data using the Ogawa PSD could be collected for ambient ozone concentrations. This paper presents an evaluation of short-term passive sampling results for nitrogen oxides (NO(x)) in El Paso and Houston, Texas, using the Ogawa PSD. The Ogawa NO(x) PSDs were compared to both Federal Reference Method (FRM) monitors and a photolytic converter, with the photolytic converter designed to report closer concentrations to "true" NO(x) by more effectively limiting the interferences of other nitrogen species. Overall, good agreement was noted for all three monitor types in both cities, supporting the potential use of lower cost Ogawa PSDs for large multi-site episodic NO(x)/NO(2)/NO saturation screening studies. This evaluation was conducted during two separate six week periods of the cooler winter months so additional testing of the Ogawa PSDs during different seasons is recommended.     

An FTIR investigation of isocyanate skin absorption using in vitro guinea pig skin

Isocyanates may cause contact dermatitis, sensitization and asthma. Dermal exposure to aliphatic and aromatic isocyanates can occur in various exposure settings. The fate of isocyanates on skin is an important unanswered question. Do they react and bind to the outer layer of skin or do they penetrate through the epidermis as unreacted compounds? Knowing the kinetics of these processes is important in developing dermal exposure sampling or decontamination strategies, as well as understanding potential health implications such exposure may have. In this paper the residence time of model isocyanates on hairless guinea pig skin was investigated in vitro using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry. Model isocyanates tested were octyl isocyanate, polymeric hexamethylene diisocyanate isocyanurate (pHDI), polymeric isophorone diisocyanate isocyanurate (pIPDI) and methylenediphenyl diisocyanate (MDI). Isocyanates in ethyl acetate (30 microL) were spiked directly on the skin to give 0.2-1.8 micromol NCO cm(-2) (NCO = -N=C=O), and absorbance of the isocyanate group and other chemical groups of the molecule were monitored over time. The ATR-FTIR findings showed that polymeric isocyanates pHDI and pIPDI may remain on the skin as unreacted species for many hours, with only 15-20% of the total isocyanate group disappearing in one hour, while smaller compounds octyl isocyanate and MDI rapidly disappear from the skin surface (80+% in 30 min). Isocyanates most likely leave the skin surface by diffusion predominantly, with minimal reaction with surface proteins. The significance of these findings and their implications for dermal exposure sampling and isocyanate skin decontamination are discussed.     

A Jackknife Approach to Examine Uncertainty and Temporal Change in the Spatial Correlation of a VOC Plume

The application of geostatistics to spatial interpolation of time-invariant properties in ground-water studies (such as transmissivity or aquifer thickness) is well documented. The use of geostatistics on time-variant conditions such as ground-water quality is also becoming more commonplace. Unfortunately, the detection of temporal changes in spatial correlation through direct comparison of experimental semivariograms is difficult due to the uncertainty in sample semivariograms constructed from field data. This paper discusses the use of the jackknife approach to estimate confidence limits of semivariograms of trichloroethane (TC) and other volatile organic compounds (VOC) in contaminated ground-water in northern Illinois. Examination of the spread of the confidence limits about the semivariograms created from two types of sampling networks are discussed.     

Spatial factors of white-tailed deer herbivory assessment in the central Appalachian Mountains

Because moderate to over-abundant white-tailed deer (Odocoileus virginianus) herbivory impacts biodiversity and can alter community function, ecological benchmarks of herbivory impact are needed to assess deer impacts. We evaluated spatial patterns of deer herbivory and their relation to herbivory assessment by evaluating woody vegetation along 20 transects at each of 30 sites spread across a wide range of deer herd densities and vegetative condition throughout the biodiverse Appalachian Mountains of Virginia, USA. Surprisingly, herbivory patterns and the availability of woody forage generally were unchanged among physiographic regions and land use diversity classes. However, some relationships between browsing pattern and vegetation varied with scale. The total quantity of vegetation browsed on a given site and at the transect scale were related positively to the availability of forage, as the proportion of stems browsed decreased as stem density increased. However, this was only true when all stems were considered equally. When stem densities by species were weighted for deer preference, the proportion of stems browsed had no relationship or increased with stem density. Compared to the value from all transects sampled, on average, the mean of ≥?3 transects within a site was within 0.1 of the browsing ratio and stem densities were within 0.5 stems m^?2. Our results suggest that one transect per square kilometer with a minimum of three transects may be sufficient for most browsing intensity survey requirements to assess herbivory impacts in the Appalachian region of Virginia. Still, inclusion of spatial factors to help partition variation of deer herbivory potentially may allow for improved precision and accuracy in the design of field herbivory impact assessment methods and improve their application across various landscape contexts.     

The MYSound Project: building an estuary-wide monitoring network for Long Island Sound,USA

A network of five water quality monitoring stations has been established in Long Island Sound, measuring temperature, salinity, and dissolved oxygen since 1999. The stations are located in areas of extreme water quality degradation (western Long Island Sound) as well as in pristine areas (eastern Long Island Sound). The data from these stations are collected every 15 minutes and posted to the project web site in real time as provisional data. After subsequent quality assurance procedures, the data are archived to the project File Transfer Protocol (FSP) site for downloading by the user community. The network of stations is in part supported logistically by a number of partners, including state and local agencies, schools, and non-governmental organizations. Data from the monitoring programs of some of these partners are also published to the project website providing a more comprehensive and complete picture of the status of the Sound than can be provided independently. This repository of information is used by marine educators, resource managers, scientists, and the general public, each with a different end purpose. We use the data from two of the stations to show that these high frequency time series measurements can be used to complement and enhance other monitoring programs within the Sound, documenting in greater detail the occurrence and duration of hypoxic events.     

Assessing Potential for Recovery of Biotic Richness and Indicator Species due to Changes in Acidic Deposition and Lake ph in Five Areas of Southeastern Canada

Biological damage to sensitive aquatic ecosystems is among the most recognisable, deleterious effects of acidic deposition. We compiled a large spatial database of over 2000 waterbodies across southeastern Canada from various federal, provincial and academic sources. Data for zooplankton, fish, macroinvertebrate (benthos) and loon species richness and occurrence were used to construct statistical models for lakes with varying pH, dissolved organic carbon content and lake size. pH changes, as described and predicted using the Integrated Assessment Model (Lam et al., 1998; Jeffries et al., 2000), were based on the range of emission reductions set forth in the Canada/US Air Quality Agreement (AQA). The scenarios tested include 1983, 1990, 1994 and 2010 sulphate deposition levels. Biotic models were developed for five regions in southeastern Canada (Algoma, Muskoka, and Sudbury, Ontario, southcentral Québec, and Kejimkujik, Nova Scotia) using regression tree, multiple linear regression and logistic regression analyses to make predictions about recovery after emission reductions. The analyses produced different indicator species in different regions, although some species showed consistent trends across regions. Generally, the greatest predicted recovery occurred during the final phase of emission reductions between 1994 and 2010 across all taxonomic groups and regions. The Ontario regions, on average, were predicted to recover to a greater extent than either southcentral Québec or the Kejimkujik area of Nova Scotia. Our results reconfirm that pH 5.5–6.0 is an important threshold below which damage to aquatic biota will remain a major local and regional environmental problem. This damage to biodiversity across trophic levels will persist well into the future if no further reductions in sulphate deposition are implemented.