Dehalogenation of polychlorinated biphenyls and polybrominated diphenyl ethers using a hybrid bioinorganic catalyst

The environmentally prevalent polybrominated diphenyl ether (PBDE) #47 and polychlorinated biphenyls (PCBs) #28 and #118 were challenged for 24 hours with a novel biomass-supported Pd catalyst (Bio-Pd(0)). Analysis of the products via GC-MS revealed the Bio-Pd(0) to cause the challenged compounds to undergo stepwise dehalogenation with preferential loss of the least sterically hindered halogen atom. A mass balance for PCB #28 showed that it is degraded to three dichlorobiphenyls (33.9%), two monochlorobiphenyls (12%), and biphenyl (30.7%). The remaining mass was starting material. In contrast, while PCB #118 underwent degradation to yield five tetra- and five trichlorinated biphenyls, no less chlorinated products or biphenyl were detected, and the total mass of degraded products was 0.3%. Although the Bio-Pd(0) material was developed for treatment of PCBs, a mass balance for PBDE #47 showed that the biocatalyst could prove a potentially useful method for treatment of PBDEs. Specifically, 10% of PBDE #47 was converted to identifiable lower brominated congeners, predominantly the tribrominated PBDE #17 and the dibrominated PBDE #4, 75% remained intact, while 15% of the starting mass was unaccounted for.     

Trends analysis of ambient 8 hour ozone and precursor monitoring data in the south central U.S

For the south central U.S., lower tropospheric ozone pollution has been a persistent and challenging problem. This paper provides long-term trends analyses of the ozone and precursor monitoring data collected over the past 20 years in four south central U.S. cities. The results of these analyses should be useful to air quality scientists, managers, planners, and modelers in assessing the effectiveness of ozone pollution control strategies being implemented or being planned for the future. Results of the data analyses show that all areas have monitored significant decreases in ozone and precursor concentrations over the past 20 years, especially in El Paso, Texas. Continuing challenges include the reduction of the percentage of time that monitors record 8 hour ozone concentrations over the U.S. 8 hour ozone standard, and the future control of highly reactive volatile organic compounds.     

Freshwater stress on small island developing states: population projections and aridity changes at 1.5 and 2 °C

Small island developing states (SIDS) face multiple threats from anthropogenic climate change, including potential changes in freshwater resource availability. Due to a mismatch in spatial scale between SIDS landforms and the horizontal resolution of global climate models (GCMs), SIDS are mostly unaccounted for in GCMs that are used to make future projections of global climate change and its regional impacts. Specific approaches are required to address this gap between broad-scale model projections and regional, policy-relevant outcomes. Here, we apply a recently developed methodology that circumvents the GCM limitation of coarse resolution in order to project future changes in aridity on small islands. These climate projections are combined with independent population projections associated with shared socioeconomic pathways (SSPs) to evaluate overall changes in freshwater stress in SIDS at warming levels of 1.5 and 2 °C above pre-industrial levels. While we find that future population growth will dominate changes in projected freshwater stress especially toward the end of the century, projected changes in aridity are found to compound freshwater stress for the vast majority of SIDS. For several SIDS, particularly across the Caribbean region, a substantial fraction (~?25%) of the large overall freshwater stress projected under 2 °C at 2030 can be avoided by limiting global warming to 1.5 °C. Our findings add to a growing body of literature on the difference in climate impacts between 1.5 and 2 °C and underscore the need for regionally specific analysis.     

A retrospective comparison of model-based forecasted PM2.5 concentrations with measurements

This study presents an assessment of the performance of the Community Multiscale Air Quality (CMAQ) photochemical model in forecasting daily PM2.5 (particulate matter < or = 2.5 microm in aerodynamic diameter) mass concentrations over most of the eastern United States for a 2-yr period from June 14, 2006 to June 13, 2008. Model predictions were compared with filter-based and continuous measurements of PM2.5 mass and species on a seasonal and regional basis. Results indicate an underprediction of PM2.5 mass in spring and summer, resulting from under-predictions in sulfate and total carbon concentrations. During winter, the model overpredicted mass concentrations, mostly at the urban sites in the northeastern United States because of overpredictions in unspeciated PM2.5 (suggesting possible overestimation of primary emissions) and sulfate. A comparison of observed and predicted diurnal profiles of PM2.5 mass at five sites in the domain showed significant discrepancies. Sulfate diurnal profiles agreed in shape across three sites in the southern portion of the domain but differed at two sites in the northern portion of the domain. Predicted organic carbon (OC) profiles were similar in shape to mass, suggesting that discrepancies in mass profiles probably resulted from the underprediction in OC. The diurnal profiles at a highly urbanized site in New York City suggested that the overpredictions at that site might be resulting from overpredictions during the morning and evening hours, displayed as sharp peaks in predicted profiles. An examination of the predicted planetary boundary layer (PBL) heights also showed possible issues in the modeling of PBL.     

Seasonal influences on PCB retention and biotransformation in fish

There is extensive evidence that fish from waters with polychlorinated biphenyls (PCB)-contaminated sediments accumulate PCBs and related chemicals and that people who eat fish from contaminated waters have higher body burdens of PCBs and PCB metabolites than those who do not. PCBs and their metabolites are potentially toxic; thus, it is important to human health to understand the uptake, biotransformation, and elimination of PCBs in fish since these processes determine the extent of accumulation. The intestinal uptake of PCBs present in the diet of fish into fish tissues is a process that is influenced by the lipid composition of the diet. Biotransformation of PCBs in fish, as in mammals, facilitates elimination, although many PCB congeners are recalcitrant to biotransformation in fish and mammals. Sequential biotransformation of PCBs by cytochrome P450 and conjugation pathways is even less efficient in fish than in mammalian species, thus contributing to the retention of PCBs in fish tissues. A very important factor influencing overall PCB disposition in fish is water temperature. Seasonal changes in water temperature produce adaptive physiological and biochemical changes in fish. While uptake of PCBs from the diet is similar in fish acclimated to winter or summer temperatures, there is evidence that elimination of PCBs occurs much more slowly when the fish is acclimated at low temperatures than at warmer temperatures. Research to date suggests that the processes of elimination of PCBs are modulated by several factors in fish including seasonal changes in water temperature. Thus, the body burden of PCBs in fish from a contaminated location is likely to vary with season.     

Migration of acidic groundwater seepage from uranium-tailings impoundments, 2. Geochemical behavior of radionuclides in groundwater

In this second paper of a series on groundwater seepage from uranium tailings, the general geochemical behavior of radionuclides is described and then applied to data from the field site, Seepage Area A of the Nordic Main impoundment near Elliot Lake, Ontario. The delineation of radionuclide behavior requires (1) the calculation of total element concentration by the summation of concentrations of each element's isotopes (the isotopic concentrations are calculated from the isotopes' radioactivities), (2) the evaluation of solid-liquid interactions using total element concentrations, and (3), for particular isotopes, the evaluation of the extent to which parental geochemical behavior causes a deviation in the isotope's behavior from that of its total element. A computerized speciation program, WATRAD, is used to evaluate aqueous complexation and mineral saturation indices of radium, actinium, thorium, and uranium. Data from Seepage Area A on isotopes of these four elements plus ²¹⁰Pb show that the geochemical behavior of radionuclides can be best defined on an individual isotopic basis rather than on an elemental basis.     

Assessing watershed transport of atrazine and nitrate to evaluate conservation practice effects and advise future monitoring strategies

Continued public support for U.S. taxpayer funded programs aimed at reducing agricultural pollutants depends on clear demonstrations of water quality improvements. The objective of this research was to determine if implementation of agricultural best management practices (BMPs) in the Goodwater Creek Experimental Watershed (GCEW) resulted in changes to atrazine and nitrate (NO₃–N) loads during storm events. An additional objective was to estimate future monitoring periods necessary to detect a 5, 10, 20, and 25% reduction in atrazine and NO₃–N event load. The GCEW is a 73 km² watershed located in northcentral Missouri, USA. Linear regressions and Akaike Information Criteria were used to determine if reductions in atrazine and NO₃–N event loads occurred as BMPs were implemented. No effects due to any BMP type were indicated for the period of record. Further investigation of event sampling from the long-term GCEW monitoring program indicated errors in atrazine load calculations may be possible due to pre-existing minimum threshold levels used to trigger autosampling and sample compositing. Variation of event loads was better explained by linear regressions for NO₃–N than for atrazine. Decommissioning of upstream monitoring stations during the study period represented a missed opportunity to further explain variation of event loads at the watershed outlet. Atrazine requires approximately twice the monitoring period relative to NO₃–N to detect future reductions in event load. Appropriate matching of pollutant transport mechanisms with autosampling protocols remains a critical information need when setting up or adapting watershed monitoring networks aimed at detecting watershed-scale BMP effects.     

Assessing coastal waters of American Samoa: territory-wide water quality data provide a critical “big-picture” view for this tropical archipelago

The coastal waters of American Samoa’s five high islands (Tutuila, Aunu’u, Ofu, Olosega, and Ta’u) were surveyed in 2004 using a probabilistic design. Water quality data were collected from the near-shore coastal habitat, defined as all near-shore coastal waters including embayments, extending out to 1/4 mile off-shore. Hydrography and water column samples were collected, and water quality data were compared to the Territorial water quality standards for pH, dissolved oxygen (DO), Enterococcus, chlorophyll a, water clarity, total nitrogen, and total phosphorus. All station measurements for pH, DO, and Enterococcus satisfied the local water quality standards, although some fraction of the Territory could not be assessed for either DO or Enterococcus. With respect to chlorophyll a, 66 ± 18% of Territory coastal waters complied with the standard, while 34 ± 18% failed to comply with the standard. For water clarity, 54 ± 18% of the Territorial waters complied with the standard while 42 ± 7% failed to comply. Territorial waters satisfied the standards for total nitrogen and phosphorus 72 ± 17% and 92 ± 10%, respectively. These data provide the first “big-picture” view of water quality in the near shore region around the high islands of American Samoa. While the picture is encouraging, these data suggest emerging water quality concerns.     

Importance of Sediment–Water Interactions in Coeur d’Alene Lake,Idaho, USA: Management Implications

A field study at Coeur dAlene Lake, Idaho, USA, was conducted between October 1998 and August 2001 to examine the potential importance of sediment–water interactions on contaminant transport and to provide the first direct measurements of the benthic flux of dissolved solutes of environmental concern in this lake. Because of potential ecological effects, dissolved zinc and orthophosphate were the solutes of primary interest. Results from deployments of an in situ flux chamber indicated that benthic fluxes of dissolved Zn and orthophosphate were comparable in magnitude to riverine inputs. Tracer analyses and benthic-community metrics provided evidence that solute benthic flux were diffusion-controlled at the flux-chamber deployment sites. That is, effects of biomixing (or bioturbation) and ground-water interactions did not strongly influence benthic flux. Remediation efforts in the river might not produce desired water-quality effects in the lake because imposed shifts in concentration gradients near the sediment–water interface would generate a benthic feedback response. Therefore, development of water-quality models to justify remediation strategies requires consideration of contaminant flux between the water column and underlying sediment in basins that have been affected by long-term (decadal) anthropogenic activities.     

SEDIMENT OXYGEN DEMAND IN THE ARROYO COLORADO RIVER1

ABSTRACT: The lower reaches of the Arroyo Colorado have historically failed to meet their use under subsection 303(b) of the U.S. Clean Water Act due to fecal coliform bacteria and low dissolved oxygen (DO). Fish kills, especially at the tidal confluence at the Port of Harlingen, Texas, have been reported. Oxygen demand from sediment (SOD) for a river typically has two states‐diffusion limited SOD (SOD) and potential SOD (pSOD), expressed when sediment is resuspended through increased flow or other disturbances. The objective of this research was to measure SOD in the Arroyo Colorado River in situ, estimate pSOD ex situ, and evaluate the relationship between SOD and the depositional environment. We measured SOD and pSOD in the Arroyo Colorado River at up to eight sites over three sampling events. We identified the sample sites based on a modified Rosgen geomorphic index for streambed stabilization. Sites with high sediment deposition potential had high SOD. The average values of SOD between sites were 0.62 g/m²/day (standard deviation 0.38 g/m²/day) and ranged from 0.13 to 1.2 g/m²/day. Potential SOD values ranged from as low as 19.2 to as high as 2,779 g/m³ sediment/ day. Potential SOD can serve as an indicator of the possible impact of SOD from resuspended sediment in stream systems.