pH dependence of ferrous sorption onto two smectite clays

This work examines the abilities of two smectite minerals (SWa-1 and Wyoming montmorillonite) to adsorb ferrous iron at concentrations from 0.037 mM (2 ppm) to 2.5 mM (240 ppm) over a range of pHs from 4.0 to 8.0. Both sorption isotherm and sorption edge data are presented. Ferrous sorption (Fe(aq)2+ = 0.1 mM) to both SWa-1 and Wyoming montmorillonite over the pH range 4.0-6.75 is relatively constant at approximately 1000 l kg(-1) for both minerals. Sorption in this pH range is attributed to the cation exchange capacity of the clay along the basal surfaces. At pH values above 6.75 the amount of ferrous iron sorbed increases dramatically. At pH 8, sorption (Fe(aq)+ = 0.1 mM) reaches 6600 l kg(-1) and 8000 l kg(-1) for Swa-1 and Wyoming montmorillonite respectively. This is attributed to the specific interaction between ferrous ions and surface sites along mineral edges. The overriding geochemical implication is that in reduced sediments containing more than a few percent clay, the pool of sorbed ferrous iron is vast. This pool of reduced iron is both redox labile and bio-available and is not readily indicated by simple measurement of dissolved Fe2+.     

Development of a hazardous air pollutants monitoring program using the Data Quality Objectives process

To effectively reduce the environmental compliance costs associated with meeting hazardous air pollutant emission requirements, the U.S. Environmental Protection Agency's Data Quality Objective (DQO) process has been proposed as a suitable framework for establishing a defensible monitoring program. Through the use of a hazardous materials pilot study, the variability in the composite vapor pressure for regulated handwipe cleaning solvents was established. These results served as inputs to the DQO process, which identified that for facility decision-makers to claim with a 99% confidence level that the facility is in compliance with the National Emission Standards for Hazardous Air Pollutants (NESHAP), a minimum of 12 handwipe cleaning solvent compliance samples (taken at random every 6 months) must have a composite vapor pressure equal to or below the regulatory limit of 45 mmHg at 20 degrees C. Implementation of the DQO-based compliance-sampling plan eliminates the need for an affected facility to sample all regulated handwipe cleaning solvents while still maintaining a reasonably high level of confidence in the compliance status of its regulated sources. The approach described for designing a defensible compliance sampling plan can be extended to other aspects of the aerospace NESHAP rule, including compliance sampling for surface coating, chemical depainting, and hazardous waste disposal.     

The estimation of PAH bioavailability in contaminated sediments using hydroxypropyl-beta-cyclodextrin and Triton X-100 extraction techniques

A study was conducted to investigate whether cyclodextrins and surfactants can be used to predict polycyclic aromatic hydrocarbon (PAH) bioavailability in contaminated sediments. Two sediment samples were extracted with aqueous solutions of hydroxypropyl-beta-cyclodextrin (HPCD) and Triton X-100. PAH removal during extraction was compared with PAH removal during biodegradation and solid-phase extraction. The latter two methods were used as reference methods to establish which part of the PAHs could be biodegraded and to what extent biodegradation was governed by bioavailability limitations. It was demonstrated that HPCD extraction followed solid-phase extraction and removed primarily readily bioavailable PAHs, while Triton X-100 extracted both readily and poorly bioavailable PAHs. Moreover, HPCD did not affect the degradation of PAHs in biodegradation experiments, while Triton X-100 enhanced the degradation of low molecular weight PAHs. It was concluded that HPCD extraction may provide a good method for the prediction of PAH bioavailability. Triton X-100 extraction is unfit for the prediction of PAH bioavailability.     

The effect of diesel fuel sulfur content on particulate matter emissions for a nonroad diesel generator

The effect of sulfur content on diesel particulate matter (DPM) emissions was studied using a diesel generator (Generac Model SD080, rated at 80 kW) as the emission source to simulate nonroad diesel emissions. A load simulator was used to apply loads to the generator at 0, 25, 50, and 75 kW, respectively. Three diesel fuels containing 500, 2100, and 3700 ppm sulfur by weight were selected as generator fuels. The U.S. Environmental Protection Agency sampling Method 5 "Determination of Particulate Matter Emissions from Stationary Sources" together with Method 1A "Sample and Velocity Traverses for Stationary Sources with Small Stacks or Ducts" was adopted as a reference method for measurement of the exhaust gas flow rate and DPM mass concentration. The effects of various parameters on DPM concentration have been studied, such as fuel sulfur contents, engine loads, and fuel usage rates. The increase of average DPM concentrations from 3.9 mg/Nm3 (n cubic meter) at 0 kW to 36.8 mg/Nm3 at 75 kW is strongly correlated with the increase of applied loads and sulfur content in the diesel fuel, whereas the fuel consumption rates are only a function of applied loads. An empirical correlation for estimating DPM concentration is obtained when fuel sulfur content and engine loads are known for these types of generators: Y = Zm(alphaX + beta), where Y is the DPM concentration, mg/m3, Z is the fuel sulfur content, ppm(w) (limited to 500-3700 ppm(w)), X is the applied load, kW, m is the constant, 0.407, alpha and beta are the numerical coefficients, 0.0118 +/- 0.0028 (95% confidence interval) and 0.4535 +/- 0.1288 (95% confidence interval), respectively.     

Modeling mercury fluxes and concentrations in a Georgia watershed receiving atmospheric deposition load from direct and indirect sources

This paper presents a modeling analysis of airborne mercury (Hg) deposited on the Ochlockonee River watershed located in Georgia. Atmospheric deposition monitoring and source attribution data were used along with simulation models to calculate Hg buildup in the subwatershed soils, its subsequent runoff loading and delivery through the tributaries, and its ultimate fate in the mainstem river. The terrestrial model calculated annual watershed yields for total Hg ranging from 0.7 to 1.1 microg/m2. Results suggest that approximately two-thirds of the atmospherically deposited Hg to the watershed is returned to the atmosphere, 10% is delivered to the river, and the rest is retained in the watershed. A check of the aquatic model results against survey data showed a reasonable agreement. Comparing observed and simulated total and methylmercury concentrations gave root mean square error values of 0.26 and 0.10 ng/L, respectively, in the water column, and 5.9 and 1 ng/g, respectively, in the upper sediment layer. Sensitivity analysis results imply that mercury in the Ochlockonee River is dominated by watershed runoff inputs and not by direct atmospheric deposition, and that methylmercury concentrations in the river are determined mainly by net methylation rates in the watershed, presumably in wetted soils and in the wetlands feeding the river.     

A salamander’s toxic arsenal: review of skin poison diversity and function in true salamanders,genus <Emphasis Type="Italic">Salamandra</Emphasis>

Terrestrial salamanders of the genus Salamandra represent one of the most prominent groups of amphibians. They are mainly distributed across Europe but also reach Northern Africa and the Near East. Members of the six currently accepted species have long been known to be poisonous; however, work on their toxins was mostly published in German language, and therefore, many nuances of these studies have remained hidden from the majority of herpetologists and toxinologists. Several Salamandra species are called fire salamanders due to their highly contrasted, black-yellow colouration which probably serves to deter predators, although thorough evidence for aposematism in Salamandra is still lacking. Salamandra skin toxins do not only represent a potent antipredator defence but may also have antimicrobial effects. A better understanding of this dual function of Salamandra skin secretions is of utmost importance in the face of the emergence of a fungal disease causing catastrophic declines of fire salamanders in Central Europe, caused by the fungus Batrachochytrium salamandrivorans. In this review, we summarize the knowledge on Salamandra toxins, providing a list of the compounds so far isolated from their secretion and focusing on the bioactivity of the major compounds in Salamandra secretions, the steroidal alkaloids. We identify priorities for future research, including a screening of co-occurrence of steroidal alkaloids and tetrodotoxins in salamandrids, chemical characterization of already identified novel steroidal compounds, elucidation of the presence and role of peptides and proteins in the secretion, and experimental in vitro and in vivo study of the interactions between bioactive compounds in Salamandra skin secretions and cutaneous fungal and bacterial pathogens.     

Establishing a Regional Monitoring Strategy: The Pacific Northwest Forest Plan

adaptive monitoring design. Adaptive monitoring design is an iterative process that refines the specifications for monitoring over time as a result of experience in implementing a monitoring program, assessing results, and interacting with users. An adaptive design therefore facilitates ecosystem management. We also discuss lessons of temporal and spatial scales raised by the consideration of a design for ecosystem management. Three additional issues—integration of information from different sources, institutional infrastructure, and the roles of individuals working in an interagency setting—are also identified, but not developed in detail.     

The Precautionary Principle and the Prevention of Marine Pollution

This paper argues that the environmental changes witnessed in the past decade call for a new approach to environmental management; an approach based not on the principle of the assimilative capacity of the environment but on the precautionary principle, and the emerging preventive environmental paradigm. Uncertainties in scientific knowledge and complexities in ecological systems have presented specific failures of the assimilative capacity methodology. It is argued that these failures are not circumstantial in nature, nor are they the result of misapplication of science by scientists. Rather, they represent inherent problems in the use of the assimilative capacity concept in environmental management. The emergence of the precautionary principle is discussed and a formulation of the principle is presented. In conjunction with the operational approach of clean production, we believe that this principle offers a sounder basis for the prevention of marine pollution in the next decade.     

Real-time quantification of mcrA, pmoA for methanogen, methanotroph estimations during composting

Composting is the controlled biological decomposition of organic matter by microorganisms during predominantly aerobic conditions. It is being increasingly adopted due to its benefits in nutrient recycling, soil reclamation, and urban land use. However, it poses an environmental concern related to its contribution to greenhouse gas production. During composting, activities of methanogenic and methanotrophic communities influence the net methane (CH4) release into the atmosphere. Using quantitative polymerase chain reaction (qPCR), this study was aimed at assessing the changes in the methyl-coenzyme M reductase (mcrA) and particulate methane monooxygenase (pmoA) copy numbers for estimation of methanogenic and methanotrophic communities, respectively. Open-windrow composting of beef cattle (Bos Taurus L.) manure with temperatures reaching > 55 degrees C was effective indegrading commensal Escherichia coli within the first week. Quantification of community DNA revealed significant differences in mcrA and pmoA copy numbers between top and middle sections. Consistent mcrA copy numbers (7.07 to 8.69 log copy number g(-1)) were detected throughout the 15-wk composting period. However, pmoA copy number varied significantly over time, with higher values during Week 0 and 1 (6.31 and 5.41 log copy number g(-1), respectively) and the lowest at Week 11 (1.6 log copy number g(-1)). Net surface CH4 emissions over the 15-wk period were correlated with higher mcrA copy number. Higher net ratio of mrA: pmoA copy numbers was observed when surface CH4 flux was high. Our results indicate that mcrA and pmoA copy numbers vary during composting and that methanogen and methanotroph populations need to be examined in conjunction with net CH4 emissions from open-windrow composting of cattle feedlot manure.