PCB Levels and Trends Within the Detroit River-Western Lake Erie Basin: A Historical Perspective of Ecosystem Monitoring

An international workshop held in the spring of 2002 convened a group of technical experts to address monitoring, modeling, and management of PCBs within the Detroit River-Western Lake Erie basin. Participants shared and discussed a diverse set of research data bases pertaining to PCB levels within the region, discussed observed changes within different components of the local ecosystem, and identified several primary issues impacting future PCB management strategies. Results presented at the workshop indicate dramatic reductions in PCB contamination levels have been observed in much of study area between the late 1970s and mid-1990s. Estimates of loadings attributable to water and atmospheric sources have generally declined, as have PCB concentrations in herring gull eggs, smelt and walleye. Nevertheless, additional improvements have not been observed during recent years and elevated contamination levels remain a concern within local hot spots, particularly in the lower Detroit River and Trenton Channel. A primary recommendation broadly supported by workshop participants is the need to maintain, support, and coordinate a comprehensive ecosystem monitoring program for the Detroit River-Western Lake Erie basin, one that incorporates both near-field and far-field monitoring elements. Such a program is crucial to provide necessary data in support of understanding ecosystem trends, calculating annual mass loadings to the system, assessing impacts of remediation actions, developing improved modeling frameworks, and formulating cost-effective management strategies for the future.     

Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends

Data are presented for polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyls ethers (PBDEs) and selected organochlorine compounds (OCs) in passive air samplers (PAS) along a rural/remote latitudinal transect from southern UK to northern Norway during 2002-2004. This study is part of an ongoing campaign, using semi-permeable membrane devices (SPMDs) as PAS over two year intervals since 1994. Data for PCBs, selected OCs and PBDEs are compared with that from previous campaigns. Absolute sequestered amounts of selected PCB congeners have decreased in a first order fashion between 1994-2004, with an average atmospheric clearance rate of 4.1 +/- 0.6 years and continue to fractionate with latitude. HCB has also declined between 1998-2004, with a clearance rate of 6 +/- 2.4 years. Data on DDT and its breakdown products indicate little fresh release in Europe. Comparison of PBDEs in 2000-02 and 2002-04 indicates site differences, generally with increases at UK sites and decreases in Norway. BDE-28, 47 and 49 decreased with increasing latitude (p < 0.04), while the other congeners did not show any significant latitudinal dependence. Transect data are presented for PAHs the first time. Three- and 4-ringed compounds dominated the mixture present in the SPMD. The PAH composition of the SPMDs at site 3 was compared to the average composition taken by active sampling at the same site. SPMD performance for sampling PAHs leaves many uncertainties, but they can be successfully used to semiquantitatively detect PAHs in the atmosphere. Fluorene and phenanthrene increased with latitude (p > 0.05), while 1-methylphenanthere, fluoranthene, benzo[b]fluoranthene and indeno[123-cd]pyrene decreased. Results are discussed in terms of sources, long-range atmospheric transport, global fractionation and clearance processes.     

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.     

Investigation of sequential and enzymatic extraction of arsenic from drinking water distribution solids using ICP-MS

A sequential extraction approach was utilized to estimate the distribution of arsenite [As(iii)] and arsenate [As(v)] on iron oxide/hydroxide solids obtained from drinking water distribution systems. The arsenic (As) associated with these solids can be segregated into three operationally defined categories (exchangeable, amorphous and crystalline) according to the sequential extraction literature. The exchangeable As, for the six drinking water solids evaluated, was estimated using 10 mM MgCl(2) and 10 mM NaH(2)PO(4) and represented between 5-34% of the total As available from the solid. The amorphously bound As was estimated using 10 mM (NH(4))(2)C(2)O(4) and represented between 57-124% of the As available from the respective solid. Finally, the crystalline bound As was estimated using titanium citrate and this represented less than 1.5% of the As associated with the solids. A synthetic stomach/intestine extraction approach was also applied to the distribution solids. The stomach fluid was found to extract between 0.5-33.3 microg g(-1) As and 120-2,360 microg g(-1) iron (Fe). The As concentrations in the intestine fluid were between 0.02-0.04 microg g(-1) while the Fe concentration ranged from 0.06-0.7 microg g(-1) for the first six drinking water distribution solids. The elevated Fe levels associated with the stomach fluid were found to produce Fe based precipitates when the intestinal treatment was applied. Preliminary observations indicate that most of the aqueous Fe in the stomach fluid is ferric ion and the observed precipitate produced in the intestine fluid is consistent with the decreased solubility of ferric ion at the pH associated with the intestine.     

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.     

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.     

Societal implications of a changing Arctic Ocean

The Arctic Ocean is undergoing rapid change: sea ice is being lost, waters are warming, coastlines are eroding, species are moving into new areas, and more. This paper explores the many ways that a changing Arctic Ocean affects societies in the Arctic and around the world. In the Arctic, Indigenous Peoples are again seeing their food security threatened and cultural continuity in danger of disruption. Resource development is increasing as is interest in tourism and possibilities for trans-Arctic maritime trade, creating new opportunities and also new stresses. Beyond the Arctic, changes in sea ice affect mid-latitude weather, and Arctic economic opportunities may re-shape commodities and transportation markets. Rising interest in the Arctic is also raising geopolitical tensions about the region. What happens next depends in large part on the choices made within and beyond the Arctic concerning global climate change and industrial policies and Arctic ecosystems and cultures.     

Reconstructed Streamflows for the Headwaters of the Wind River,Wyoming, United States1

Abstract: Tree rings offer a means to extend observational records of streamflow by hundreds of years, but dendrohydrological techniques are not regularly applied to small tributary and headwaters gages. Here we explore the potential for extending three such gage records on small streams in the Wind River drainage of central Wyoming, United States. Using core samples taken from Douglas fir (Pseudotsuga menziesii), piñon pine (Pinus edulis), and limber pine (Pinus flexilis) at 38 sites, we were able to reconstruct streamflows for the headwaters of the Wind River back to 1672 AD or earlier. The streamflow reconstructions for Bull Lake Creek above Bull Lake; the Little Popo Agie River near Lander, Wyoming; and Wind River near Dubois, Wyoming explained between 40% and 64% of the observed variance, and these extended records performed well in a variety of statistical verification tests. The full reconstructions show pronounced inter‐annual variability in streamflow, and these proxy records also point to the prevalence of severe, sustained droughts in this region. These reconstructions indicate that the 20th Century was relatively wet compared to previous centuries, and actual gage records may capture only a limited subset of potential natural variability in this area. Further analyses reveal how tree‐ring based reconstructions for small tributary and headwaters gages can be strongly influenced by the length and quality of calibration records, but this work also demonstrates how the use of a spatially extensive network of tree‐ring sites can improve the quality of these types of reconstructions.     

Spatial Variability of Nitrate Concentrations Under Diverse Conditions in Tributaries to a Lake Watershed1

Abstract: Nitrate‐nitrogen (NO₃‐N) concentrations in stream water often respond uniquely to changes in inter‐annual conditions (e.g., biological N uptake and precipitation) in individual catchments. In this paper, we assess (1) how the spatial distribution of NO₃‐N concentrations varies across a dense network of nonnested catchments and (2) how relationships between multiple landscape factors [within whole catchments and hydrologically sensitive areas (HSAs) of the catchments] and stream NO₃‐N are expressed under a variety of annual conditions. Stream NO₃‐N data were collected during two synoptic sampling events across >55 tributaries and two synoptic sampling periods with >11 tributaries during summer low flow periods. Sample tributaries drain mixed land cover watersheds ranging in size from 0.150 to 312 km² and outlet directly to Cayuga Lake, New York. Changes in NO₃‐N concentration ratios between each sampling event suggest a high degree of spatial heterogeneity in catchment response across the Cayuga Lake Watershed, ranging from 0.230 to 61.4. Variations in NO₃‐N concentrations within each of the large synoptic sampling events were also high, ranging from 0.040 to 8.7 mg NO₃‐N/l (March) and 0.090 to 15.5 mg NO₃‐N/l (October). Although Pearson correlation coefficients suggest that this variability is related to multiple landscape factors during all four sampling events, partial correlations suggest percentage of row crops in the catchments as the only similar factor in March and October and catchment area as the only factor during summer low flows. Further, the strength of the relationships is typically lower in the HSAs of catchment. Advancing current understanding of such variations and relationships to landscape factors across multiple catchments – and under a variety of biogeochemical and hydrological conditions – is important, as (1) nitrate continues to be employed as an indicator of regional aquatic ecosystem health and services and (2) a unified framework approach for understanding individual catchment processes is a rapidly evolving focus for catchment‐based science and management.     

Daily Updating of Operational Statistical Seasonal Water Supply Forecasts for the western U.S.1

Abstract: Official seasonal water supply outlooks for the western United States are typically produced once per month from January through June. The Natural Resources Conservation Service has developed a new outlook product that allows the automated production and delivery of this type of forecast year‐round and with a daily update frequency. Daily snow water equivalent and water year‐to‐date precipitation data from multiple SNOTEL stations are combined using a statistical forecasting technique (“Z‐Score Regression”) to predict seasonal streamflow volume. The skill of these forecasts vs. lead‐time is comparable to the official published outlooks. The new product matches the intra‐monthly trends in the official forecasts until the target period is partly in the past, when the official forecasts begin to use information about observed streamflows to date. Geographically, the patterns of skill also match the official outlooks, with highest skill in Idaho and southern Colorado and lowest skill in the Colorado Front Range, eastern New Mexico, and eastern Montana. The direct and frequent delivery of objective guidance to users is a significant new development in the operational hydrologic seasonal forecasting community.