Ultraviolet irradiation effects incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter

One of the concerns regarding the safety and efficacy of ultraviolet radiation for treatment of drinking water and wastewater is the fate of nitrate, particularly its photolysis to nitrite. In this study, N NMR was used to establish for the first time that UV irradiation effects the incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter (NOM). Irradiation of (15)N-labeled nitrate in aqueous solution with an unfiltered medium pressure mercury lamp resulted in the incorporation of nitrogen into Suwannee River NOM (SRNOM) via nitrosation and other reactions over a range of pH from approximately 3.2 to 8.0, both in the presence and absence of bicarbonate, confirming photonitrosation of the NOM. The major forms of the incorporated label include nitrosophenol, oxime/nitro, pyridine, nitrile, and amide nitrogens. Natural organic matter also catalyzed the reduction of nitrate to ammonia on irradiation. The nitrosophenol and oxime/nitro nitrogens were found to be susceptible to photodegradation on further irradiation when nitrate was removed from the system. At pH 7.5, unfiltered irradiation resulted in the incorporation of (15)N-labeled nitrite into SRNOM in the form of amide, nitrile, and pyridine nitrogen. In the presence of bicarbonate at pH 7.4, Pyrex filtered (cutoff below 290-300 nm) irradiation also effected incorporation of nitrite into SRNOM as amide nitrogen. We speculate that nitrosation of NOM from the UV irradiation of nitrate also leads to production of nitrogen gas and nitrous oxide, a process that may be termed photo-chemodenitrification. Irradiation of SRNOM alone resulted in transformation or loss of naturally abundant heterocyclic nitrogens.     

The Harvest and Management of Migratory Bird Eggs by Inuit in Nunatsiavut, Labrador

This paper presents the results of collaborative research conducted in 2007 on the harvest of migratory bird eggs by Inuit households of Nunatsiavut, Labrador. Harvest variability between communities and species is examined, as is the social and ecological factors affecting the 2007 Inuit egg harvest. Representing the first comprehensive account of Inuit egg use in Labrador, this information should be valuable to agencies responsible for managing migratory bird populations in North America and will contribute to a more informed understanding of the complexity and temporal variability in subsistence harvesting among Labrador Inuit. It is argued that the recognition of this complexity will be critical as the Nunatsiavut Government and other wildlife management agencies formulate management policies that are supportive rather, than constraining, to Inuit resource use in the future.     

Putting humans in ecology: consistency in science and management

Normal and abnormal levels of human participation in ecosystems can be revealed through the use of macro-ecological patterns. Such patterns also provide consistent and objective guidance that will lead to achieving and maintaining ecosystem health and sustainability. This paper focuses on the consistency of this type of guidance and management. Such management, in sharp contrast to current management practices, ensures that our actions as individuals, institutions, political groups, societies, and as a species are applied consistently across all temporal, spatial, and organizational scales. This approach supplants management of today, where inconsistency results from debate, politics, and legal and religious polarity. Consistency is achieved when human endeavors are guided by natural patterns. Pattern-based management meets long-standing demands for enlightened management that requires humans to participate in complex systems in consistent and sustainable ways.     

Assigning concentration values for dioxin and furan congeners in human serum when measurements are below limits of detection: an observational approach

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in dietary sources for humans have been declining over the previous two decades. These declines have been accompanied by decreases in concentrations of these compounds in humans, as evidenced by measurements in blood and milk. Because of the decreasing concentrations of PCDD/PCDFs in the environment and in humans, measuring PCDD/PCDF congeners in humans has become increasingly difficult, despite advances in analytic methods. An observational approach was recently described to address the quandary of non-detectable results in determining toxic equivalents. This approach, called the congener ratio approach, is specifically for cases where concentrations of 2,3,7,8-TCDD (TCDD) are below the limit of detection (LOD), and where concentrations of 1,2,3,7,8-pentachlorodibenzo-p-dioxin (PeCDD) are equal to or above the LOD. Development of this approach relied on evaluating data on measured concentrations of TCDD and PeCDD in human serum from the general population. The congener ratio approach for TCDD and PeCDD was based on the concentration of TCDD being approximately 40% that of PeCDD in serum from the general population. Additional analyses presented here reveal that when concentrations of both congeners are above the LOD, the data appear to generally support the congener ratio approach for TCDD and PeCDD, with the caveat that gender may affect the ratio. However, the TCDD/PeCDD relation is less clear when TCDD is less than the LOD; in this situation, the relation overpredicts levels of TCDD approximately 80% of the time for the 2001-2002 NHANES database. Using the congener ratio approach for other PCDD/PCDF congeners requires assessing the correlation and the frequency of detection for both TCDD and PeCDD.     

Calculation of serum "total lipid" concentrations for the adjustment of persistent organohalogen toxicant measurements in human samples

Persistent organohalogen toxicants such as 2,3,7,8-tetrachlorodibenzo-p-dioxin or polychlorinated biphenyls measured in human serum are often expressed on a lipid weight basis, most commonly by dividing the toxicants' concentration by the weight of total lipids in the sample. Therefore, the manner in which this lipid adjustment is calculated may influence the final reported result. Gravimetric total lipid assays have been used, but they are time-consuming and sometimes may be ill-defined. Consequently, alternative methods using enzymatic assays have been developed based on summing the individual lipid species measured. Recent reports, however, have suggested that significantly different total lipid results may be obtained when using alternative formulae in a summation approach. In this report, we summarize the results obtained from lipid measurements of nearly 900 samples made as part of a study of a group of older American men (mean age 62 years), and we compare our total lipid estimates obtained by using both our standard and "short" formula (the latter based on total cholesterol and triglycerides only) with results obtained using the recently proposed alternative formulae. Our findings indicate that both our long and short formulae provide similar estimates of serum total lipid concentrations, and that differences observed in lipid estimates when using the newer alternative summation methods may reflect differences in how the term "total lipid" is defined, especially with regard to the need to include the contribution of the weight of the cholesterol ester fatty acids in the calculation.     

Macroinvertebrate Assemblages on Woody Debris and Their Relations with Environmental Variables in the Lower Sacramento and San Joaquin River Drainages, California

Data from 25 sites were used to evaluate associations between macroinvertebrate assemblages on large woody debris (snags) and environmental variables in the lower San Joaquin and Sacramento River drainages in California as part of the U.S. Geological Survey's National Water Quality Assessment Program. Samples were collected from 1993 to 1995 in the San Joaquin River drainage and in 1996 and 1997 in the Sacramento River drainage. Macroinvertebrate taxa were aggregated to the family (or higher) level of taxonomic organization, resulting in 39 taxa for analyses. Only the 31 most common taxa were used for two-way indicator species analysis (TWINSPAN) and canonical correspondence analysis (CCA). TWINSPAN analysis defined four groups of snag samples on the basis of macroinvertebrate assemblages. Analysis of variance identified differences in environmental and biotic characteristics among the groups. These results combined with the results of CCA indicated that mean dominant substrate type, gradient, specific conductance, water temperature, percentage of the basin in agricultural land use, percentage of the basin in combined agricultural and urban land uses, and elevation were important factors in explaining assemblage structure. Macroinvertebrate assemblages on snags may be useful in family level bioassessments of environmental conditions in valley floor habitats.     

Design and Verification of a Programmable Gas Dispensing System for Exposing Plants to Dynamic Concentrations of Air Pollutants

Abstract

Landfills represent a source of distributed emissions source over an irregular and heterogeneous surface. In the method termed “Other Test Method-10” (OTM-10), the U.S. Environmental Protection Agency (EPA) has proposed a method to quantify emissions from such sources by the use of vertical radial plume mapping (VRPM) techniques combined with measurement of wind speed to determine the average emission flux per unit area per time from nonpoint sources. In such application, the VRPM is used as a tool to estimate the mass of the gas of interest crossing a vertical plane. This estimation is done by fitting the field-measured concentration spatial data to a Gaussian or some other distribution to define a plume crossing the vertical plane. When this technique is applied to landfill surfaces, the VRPM plane may be within the emitting source area itself. The objective of this study was to investigate uncertainties associated with using OTM-10 for landfills. The spatial variability of emission in the emitting domain can lead to uncertainties of –34 to 190% in the measured flux value when idealistic scenarios were simulated. The level of uncertainty might be higher when the number and locations of emitting sources are not known (typical field conditions). The level of uncertainty can be reduced by improving the layout of the VRPM plane in the field in accordance with an initial survey of the emission patterns. The change in wind direction during an OTM-10 testing setup can introduce an uncertainty of 20% of the measured flux value. This study also provides estimates of the area contributing to flux (ACF) to be used in conjunction with OTM-10 procedures. The estimate of ACF is a function of the atmospheric stability class and has an uncertainty of 10–30%.     

Research and Evaluation of Organic Hazardous Air Pollutant Source Emission Test Methods

Abstract

Title III of the Clean Air Act Amendments of 1990 has increased the need for well defined and tested stationary source emission sampling and analysis methods. The Methods Branch of the Air Measurements Research Division of U.S. EPA's Office of Research and Development is responsible for a major methods development and evaluation program intended to help fill that need. This paper summarizes recent developments from several of the component projects of that program. Primary emphasis is placed on status and references for methods for organic hazardous air pollutants, such as phosgene, methanol, chloroform, acetonitrile, isocyanates, aldehydes, halogenated organics, non-halogenated organics, and volatile organic material     

Pilot-Scale Evaluation of an Incinerability Ranking System for Hazardous Organic Compounds

The U.S. Environmental Protection Agency’s (EPA) hazardous waste incinerator performance standards specify a minimum destruction and removal efficiency (DRE) for principal organic hazardous constituents (POHCs) designated in the incinerator waste feed. In the past, selection of appropriate POHCs for incinerator trial burns has been based largely on their heats of combustion. Attempting to improve upon this approach, the University of Dayton Research Institute (UDRI), under contract to the EPA Risk Reduction Engineering Laboratory, has developed a thermal stability-based ranking of compound "incinerability". The subject study was conducted to evaluate the laboratory-developed ranking system in a pilot-scale incinerator.

Mixtures of POHCs, spanning the ranking scale from most- to least-difficult to destroy (Class 1 to Class 7, respectively), were prepared and combined with a clay-based sorbent matrix. These mixtures were then fed into the rotary kiln incineration system at the U.S. EPA Incineration Research Facility (IRF). In a series of five tests, the following conditions were evaluated: baseline/ typical operation; thermal failure (quenching); mixing failure (overcharging); matrix failure (low feed H/CI ratio); and a worst-case combination of the three failure modes.

Under baseline conditions, mixing failure, and matrix failure, kiln-exit DREs for each compound were comparable from test to test. Operating conditions in these 3 modes appeared to be sufficient to effect considerable destruction (greater than 99.99 percent DRE) of all compounds. As a result, separation of the highest-ranked POHCs from the lowest-ranked POHCs according to observed DRE was not possible; a correlation between POHC ranking and DRE could not be confirmed.

A correlation between predicted and observed incinerability was more evident for the thermal failure and worst-case conditions. Kiln-exit DREs for the four POHCs predicted to be most stable (those in Classes 1 and 2) ranged from 99% to 99.99% under these conditions, and were generally lower than DREs for the POHCs predicted to be more easily destroyed. Statistically significant correlations above the 99 percent and 93 percent confidence intervals were identified for the thermal-failure and worst-case tests, respectively.