Degradation of the herbicide dichlobenil and its metabolite BAM in soils and subsurface sediments

The worldwide used herbicide dichlobenil (2,6-dichlorobenzonitrile) has resulted in widespread presence of its metabolite 2,6-dichlorobenzamide (BAM) in surface water and groundwater. To evaluate the potential for natural attenuation of this BAM pollution in groundwater, we studied the degradation of BAM and dichlobenil in 16 samples of clayey till, unconsolidated sand and limestone, including sediments from both oxidized and reduced conditions. The degradation of dichlobenil occurred primarily in the upper few meters below surface, although dichlobenil was strongly sorbed to these sediments. However, the degradation of dichlobenil to BAM could not be correlated to either sorption, water chemistry, composition of soils or sediments. Degradation of dichlobenil to BAM was limited (<2% degraded) in the deeper unsaturated zones, and no degradation was observed in aquifer sediments. This illustrates, that dichlobenil transported to aquifers does not contribute to the BAM-contamination in aquifers. A small, but significant degradation of BAM was observed in the upper part of the unsaturated zones in sandy sediments, but no degradation was observed in the clayey till sediment or in the deeper unsaturated zones. The insignificant degradation of BAM in aquifer systems shows that BAM pollution detected in aquifers will appear for a long time; and consequently the potential for natural attenuation of BAM in aquifer systems is limited.     

Use of n-fold cross-validation to evaluate three methods to calculate heavy truck annual average daily traffic and vehicle miles traveled

Reliable estimates of heavy-truck volumes in the United States are important in a number of transportation applications including pavement design and management, traffic safety, and traffic operations. Additionally, because heavy vehicles emit pollutants at much higher rates than passenger vehicles, reliable volume estimates are critical to computing accurate inventories of on-road emissions. Accurate baseline inventories are also necessary to forecast future scenarios. The research presented in this paper evaluated three different methods commonly used by transportation agencies to estimate annual average daily traffic (AADT), which is used to determine vehicle miles traveled (VMT). Traffic data from continuous count stations provided by the Iowa Department of Transportation were used to estimate AADT for single-unit and multiunit trucks for rural freeways and rural primary highways using the three methods. The first method developed general expansion factors, which apply to all vehicles. AADT, representing all vehicles, was estimated for short-term counts and was multiplied by statewide average truck volumes for the corresponding roadway type to obtain AADT for each truck category. The second method also developed general expansion factors and AADT estimates. Truck AADT for the second method was calculated by multiplying the general AADT by truck volumes from the short-term counts. The third method developed expansion factors specific to each truck group. AADT estimates for each truck group were estimated from short-term counts using corresponding expansion factors. Accuracy of the three methods was determined by comparing actual AADT from count station data to estimates from the three methods. Accuracy of the three methods was compared using n-fold cross-validation. Mean squared error of prediction was used to estimate the difference between estimated and actual AADT. Prediction error was lowest for the method that developed separate expansion factors for trucks. Implications for emissions estimation using the different methods are also discussed.     

Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.     

Synthesis of polyhydroxyalkanoates in municipal wastewater treatment.

Biologically derived polyesters known as polyhydroxyalkanoates (PHAs) represent a potentially "sustainable" replacement to fossil-fuel-based thermoplastics. However, current commercial practices that produce PHA with pure microbial cultures grown on renewable, but refined, feedstocks (i.e., glucose) under sterile conditions do not represent a sustainable commodity. Here, we report on PHA production with a mixed microbial consortium indigenous to an activated sludge process on carbon present in municipal wastewaters. Reactors operated under anaerobic/aerobic and aerobic-only mode and fed primary solids fermenter liquor maintained a mixed microbial consortium capable of synthesizing PHA at 10 to 25% (w/w), while reducing soluble COD by approximately 62 to 71%. More critically, an aerobic batch reactor seeded from the anaerobic/aerobic reactor and fed fermenter liquor achieved approximately 53% PHA (w/w). Results presented suggest that environmentally benign production of biodegradable polymers is feasible. We further used PHA-rich biomass to produce a natural fiber-reinforced thermoplastic composite that can be used to offset advanced wastewater treatment costs.     

Fugitive emissions opacity determination using the digital opacity compliance system (DOCS)

Maintenance of Department of Defense (DoD) weapon systems, conducting battlefield training exercises as well as meeting military construction and/or demolition schedules, invariably generate fugitive air emissions, many of which are visible. Although there is no codified federal method for quantifying fugitive emissions opacity, many state and local air regulatory agencies have instituted enforceable fugitive emission opacity standards at DoD facilities. The current study focused on comparing the performance of the digital opacity compliance system (DOCS) with U.S. Environment Protection Agency Method 9 (Method 9) certified human observers in quantifying the visible opacity associated with fugitive emissions produced using a commercial fog generator. By systematically repositioning both DOCS cameras and Method 9-certified observers during field testing, differences in method performance as a function of observational locations were documented. At both the 30- and 300-ft off-set distances, opacity levels reported by the DOCS technology and Method 9-certified smoke readers were found to be statistically different at the 99% confidence level. Alternatively, at the 90- and 150-ft off-set distances, results suggested that there was an insignificant difference at the 99% confidence level between the two methods. Comparing the magnitude of the each method's standard deviation suggested that, at the 30-ft off-set distance, the DOCS technology was consistently more precise than Method 9-certified readers regardless of the observer's downwind distance. However, at the 90, 150, and 300-ft off-set distances, method precision seemed to vary as a function of both off-set and downwind distance. The primary factor affecting the consistency in opacity measurements appeared to be the impact of ground-level air turbulence on fog plume dispersion and transport. Field observations demonstrated that localized wind shear played a critical and decisive role in how and to what extent fugitive emissions opacity could be determined, regardless of the method selected.     

Source apportionment of fine particles in Tennessee using a source-oriented model

Source apportionment of fine particles (PM2.5, particulate matter < 2 microm in aerodynamic diameter) is important to identify the source categories that are responsible for the concentrations observed at a particular receptor. Although receptor models have been used to do source apportionment, they do not fully take into account the chemical reactions (including photochemical reactions) involved in the formation of secondary fine particles. Secondary fine particles are formed from photochemical and other reactions involving precursor gases, such as sulfur dioxide, oxides of nitrogen, ammonia, and volatile organic compounds. This paper presents the results of modeling work aimed at developing a source apportionment of primary and secondary PM2.5. On-road mobile source and point source inventories for the state of Tennessee were estimated and compiled. The national emissions inventory for the year 1999 was used for the other states. U.S. Environmental Protection Agency Models3/Community Multi-Scale Air Quality modeling system was used for the photochemical/secondary particulate matter modeling. The modeling domain consisted of a nested 36-12-4-km domain. The 4-km domain covered the entire state of Tennessee. The episode chosen for the modeling runs was August 29 to September 9, 1999. This paper presents the approach used and the results from the modeling and attempts to quantify the contribution of major source categories, such as the on-road mobile sources (including the fugitive dust component) and coal-fired power plants, to observed PM2.5 concentrations in Tennessee. The results of this work will be helpful in policy issues targeted at designing control strategies to meet the PM2.5 National Ambient Air Quality Standards in Tennessee.     

International trade in meat: the tip of the pork chop

This paper provides an original account of global land, water, and nitrogen use in support of industrialized livestock production and trade, with emphasis on two of the fastest-growing sectors, pork and poultry. Our analysis focuses on trade in feed and animal products, using a new model that calculates the amount of "virtual" nitrogen, water, and land used in production but not embedded in the product. We show how key meat-importing countries, such as Japan, benefit from "virtual" trade in land, water, and nitrogen, and how key meat-exporting countries, such as Brazil, provide these resources without accounting for their true environmental cost. Results show that Japan's pig and chicken meat imports embody the virtual equivalent of 50% of Japan's total arable land, and half of Japan's virtual nitrogen total is lost in the US. Trade links with China are responsible for 15% of the virtual nitrogen left behind in Brazil due to feed and meat exports, and 20% of Brazil's area is used to grow soybean exports. The complexity of trade in meat, feed, water, and nitrogen is illustrated by the dual roles of the US and The Netherlands as both importers and exporters of meat. Mitigation of environmental damage from industrialized livestock production and trade depends on a combination of direct-pricing strategies, regulatory approaches, and use of best management practices. Our analysis indicates that increased water- and nitrogen-use efficiency and land conservation resulting from these measures could significantly reduce resource costs.     

Closed cycle construction: an integrated process for the separation and reuse of C&D waste

In The Netherlands, construction and demolition (C&D) waste is already to a large extent being reused, especially the stony fraction, which is crushed and reused as a road base material. In order to increase the percentage of reuse of the total C&D waste flow to even higher levels, a new concept has been developed. In this concept, called 'Closed Cycle Construction', the processed materials are being reused at a higher quality level and the quantity of waste that has to be disposed of is minimised. For concrete and masonry, the new concept implies that the material cycle will be completely closed, and the original constituents (clay bricks, gravel, sand, cement stone) are recovered in thermal processes. The mixed C&D waste streams are separated and decontaminated. For this purpose several dry separation techniques are being developed. The quality of the stony fraction is improved so much, that this fraction can be reused as an aggregate in concrete. The new concept has several benefits from a sustainability point of view, namely less energy consumption, less carbon dioxide emission, less waste production and less land use (for excavation and disposal sites). One of the most remarkable benefits of the new concept is that the thermal process steps are fuelled with the combustible fraction of the C&D waste itself. Economically the new process is more or less comparable with the current way of processing C&D waste. On the basis of the positive results of a feasibility study, currently a pilot and demonstration project is being carried out. The aim is to optimise the different process steps of the Closed Cycle Construction process on a laboratory scale, and then to verify them on a large scale. The results of the project are promising, so far.     

Reusing fly ash in glass fibre reinforced cement: a new generation of high-quality GRC composites

New composite materials based on an alkali-resistant glass-fibre reinforced cement (AR-GRC) system are being developed by using fly ash (FA) produced at coal thermoelectric power plants, and fluid catalytic cracking catalyst residue (FC3R) from the petrol industry as cement replacement materials. These wastes are reactive from the pozzolanic viewpoint, and modify the nature and the microstructure of the cement matrix when a part of the Portland cement is replaced in the formulation of GRC. Several microstructural and mechanical aspects are being studied for AR-GRC systems. The behaviour of composites exposed to ageing shows that the pozzolanic activity of the ground FA added in high amounts and its mixture with the FC3R increase the flexural strength and no evidences of strength decay are observed. Additionally, the fibres due to the high alkalinity of the cementing matrix can be deteriorated. Fibres in the control (only Portland cement) and FC3R containing composites were attacked, whereas composites with FA and their mixture with FC3R show that the fibres have not been attacked, due to the pozzolanic activity of replacing materials that reduce the calcium hydroxide content in the cementing matrix.     

Management options and effects on a marine ecosystem: assessing the future of the Baltic

We are using the coupled models in a decision support system, Nest, to evaluate the response of the marine ecosystem to changes in external loads through various management options. The models address all the seven major marine basins and the entire drainage basin of the Baltic Sea. A series of future scenarios have been developed, in close collaboration with the Helsinki Commission, to see the possible effects of improved wastewater treatment and manure handling, phosphorus-free detergents, and less intensive land use and live stocks. Improved wastewater treatment and the use of phosphorus-free detergents in the entire region would drastically decrease phosphorus loads and improve the marine environment, particularly the occurrence of cyanobacterial blooms. However, the Baltic Sea will remain eutrophic, and to reduce other effects, a substantial reduction of nitrogen emissions must be implemented. This can only be obtained in these scenarios by drastically changing land use. In a final scenario, we have turned 50% of all agricultural lands into grasslands, together with efficient wastewater treatments and a ban of phosphorus in detergents. This scenario will substantially reduce primary production and the extension of hypoxic bottoms, increase water transparency in the most eutrophied basins, and virtually eliminate extensive cyanobacterial blooms.