Linking ground-water age and chemistry data along flow paths: implications for trends and transformations of nitrate and pesticides

Tracer-based ground-water ages, along with the concentrations of pesticides, nitrogen species, and other redox-active constituents, were used to evaluate the trends and transformations of agricultural chemicals along flow paths in diverse hydrogeologic settings. A range of conditions affecting the transformation of nitrate and pesticides (e.g., thickness of unsaturated zone, redox conditions) was examined at study sites in Georgia, North Carolina, Wisconsin, and California. Deethylatrazine (DEA), a transformation product of atrazine, was typically present at concentrations higher than those of atrazine at study sites with thick unsaturated zones but not at sites with thin unsaturated zones. Furthermore, the fraction of atrazine plus DEA that was present as DEA did not increase as a function of ground-water age. These findings suggest that atrazine degradation occurs primarily in the unsaturated zone with little or no degradation in the saturated zone. Similar observations were also made for metolachlor and alachlor. The fraction of the initial nitrate concentration found as excess N2 (N2 derived from denitrification) increased with ground-water age only at the North Carolina site, where oxic conditions were generally limited to the top 5 m of saturated thickness. Historical trends in fluxes to ground water were evaluated by relating the times of recharge of ground-water samples, estimated using chlorofluorocarbon concentrations, with concentrations of the parent compound at the time of recharge, estimated by summing the molar concentrations of the parent compound and its transformation products in the age-dated sample. Using this approach, nitrate concentrations were estimated to have increased markedly from 1960 to the present at all study sites. Trends in concentrations of atrazine, metolachlor, alachlor, and their degradates were related to the timing of introduction and use of these compounds. Degradates, and to a lesser extent parent compounds, were detected in ground water dating back to the time these compounds were introduced.     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.     

Is adaptive management helping to solve fisheries problems?

Adaptive management has been widely recommended as a way to deal with extreme uncertainty in natural resource and environmental decision making. The core concept in adaptive management is that policy choices should be treated as deliberate, large-scale experiments; hence, policy choice should be treated at least partly as a problem of scientific experimental design. There have now been upwards of 100 case studies where attempts were made to apply adaptive management to issues ranging from restoration of endangered desert fish species to protection of the Great Barrier Reef. Most of these cases have been failures in the sense that no experimental management program was ever implemented, and there have been serious problems with monitoring programs in the handful of cases where an experimental plan was implemented. Most of the failures can be traced to three main institutional problems: i) lack of management resources for the expanded monitoring needed to carry out large-scale experiments; ii) unwillingness by decision makers to admit and embrace uncertainty in making policy choices; and iii) lack of leadership in the form of individuals willing to do all the hard work needed to plan and implement new and complex management programs.     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 2-Polychlorinated biphenyls

The temporal variability and bioaccumulation dynamics of individual PCBs were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the polluted Buenos Aires coastal area. Fish muscles contain high concentrations of total PCBs (11+/-7.2, 4.6+/-3.4 or 19+/-13 microg g(-1), dry, fresh and lipid weight, respectively) reflecting chronic bioaccumulation from sewage-industrial particulates. On a temporal basis, lipid normalized PCBs concentrations peaked by the end of 2001-2002 coincident with the rainiest period over the last four decades and shortly after PCB prohibition in the country, reflecting massive discharges to the coastal ecosystem. PCB composition in fish muscles show a prevailing contribution of hexachlorobiphenyls (35+/-4.2%), followed by hepta (23+/-3.0%), penta (20+/-3.6%), tri-tetra (16+/-4.8%) and minor proportions of octa-decachlorobiphenyls (5.7+/-3.1%) similar to an Aroclor 1242-1254-1260 1:2:4 mixture. During 2001-2002 maxima fish showed an enrichment in tri-tetrachlorobiphenyls ( approximately 1242-1254-1260 1:1:1 mixture) denoting a fresher signature. Fish/settling material lipid-organic carbon accumulation factors (BSAFs: 2.4-46, average: 21+/-10) plotted against kow showed a parabolic trend (BSAFs=-0.38 log kow2 + 5.16 log kow -15.85; R2=0.46) maximizing at hexa, hepta and octachlorobiphenyl 203 with reduced bioaccumulation of a few hepta (170, 191) and most octa-decachlorobihenyls suggesting limited intestinal absorption.     

A synchronized amphibian metamorphosis assay as an improved tool to detect thyroid hormone disturbance by endocrine disruptors and apolar sediment extracts

Amphibian metamorphosis assays are used to evaluate potential effects of endocrine disrupting compounds on the thyroid hormone axis. In this study, Xenopus laevis tadpoles are kept in a solution of 0.2% thiourea (TU) to arrest and synchronise them in their development. The advantage of this synchronized amphibian metamorphosis assays is that synchronised tadpoles are available at any time to start metamorphosis experiments, and experimental groups are much more homogenous at the start of experimental exposure compared with groups selected from an untreated pool of animals. The water volume per animal was kept constant throughout the experimental period to overcome the influence of declining numbers of animals per aquarium due to metamorphosis and mortality on the density dependent development of the remaining tadpoles. Clophen A50 (a technical PCB mixture), the single congener 3,3',4,4'-tetrachlorobiphenyl (PCB 77) and apolar sediment extracts that were previously tested positive in the T-Screen, an in vitro proliferation assay for thyroid hormone disruption, were tested in the Synchronized Amphibian Metamorphosis Assay. Endpoints studied were mortality, malformations, body weight, and percentage of metamorphosed froglets at the end of the 60-day experimental period, percentage of tadpoles in different developmental stages, and developmental stage-dependent awarded penalty points. Dietary exposure to Clophen A50 (0.2-50mg/kg food) resulted in a significant increased percentage of tadpoles that did not pass metamorphosis at concentrations higher than 2mg/kg food. Time until metamorphosis in those animals that were able to metamorphose after the 60-days experimental period was significantly decreased. Dietary exposure to PCB 77, a congener that can be readily metabolised, did not result in significant effects in any exposure group (2-500 microg/kg food). Apolar sediment extracts from two of the three sites that are contaminated with a wide variety of chemicals significantly decreased the percentage of metamorphosed animals and significantly increased the number of tadpoles that remained in early and late metamorphic stages. These effects already occurred when the extracts where diluted more than 1000 times (on an organic carbon base) compared to environmental concentrations. The rank of potency was comparable to results obtained with the T-screen. This suggests the presence of thyroid hormone disrupting compounds in the aquatic environment and possible effects of such compounds on animal development in the wild.     

The case for variable density: a new perspective on activated sludge settling.

A new, simple method for directly measuring activated sludge density was developed and applied, and the effects of biomass density on activated sludge settling in full-scale systems were evaluated. The driving force of sedimentation is the physical weight of the biological solids, but the role of biomass density in sedimentation has been largely ignored. Biomass density varied amongst treatment systems and this variability was correlated with settleability. Floc densities were approximately normally distributed within individual samples. Nonsoluble phosphorus content was a major contributor to density, and plants with enhanced biological phosphorus removal (EBPR) configurations generally had higher densities and better settleability than non-EBPR plants with similar filament contents. These results suggest that future work may benefit from consideration of density as a factor affecting activated sludge settling.     

Catalyst deterioration over the lifetime of small utility engines

In this paper, the deterioration of catalysts in small, four-stroke, spark-ignition engines is described. The laboratory testing performed followed a proven test method that mimics the lifetime of a small air-cooled utility engine operating under normal field conditions. The engines used were single-cylinder, 6.5-hp, side-valve engines. These engines have a nominal 125-hr lifetime. The effectiveness of the catalysts was determined by testing exhaust emissions before and after the catalyst to determine the catalyst's efficiency. This was done several times during the lifetime of the engines to determine the deterioration in the performance of the catalysts at lowering pollutant emissions. Additional testing was performed on the catalysts to determine wear patterns, contamination, and recoverable activity. The results indicate that considerable catalyst deterioration is occurring over the lifetime of the engine. The results reveal that soot buildup, poisons, and active surface loss appear to be the contributing factors to the deterioration. These results were determined after analyzing the exhaust emissions data, scanning electron microscope results analysis, and the impact of regeneration attempts. An ANOVA statistical analysis was performed, and it was determined that the emissions are also impacted, to some degree, by time and the engine itself.     

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.     

Size and composition distributions of particulate matter emissions: part 1--light-duty gasoline vehicles

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965-2003; odometer readings 1264-207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-microm aerodynamic diameter) and fine PM1.8 (< or =1.8-microm aerodynamic diameter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emissions of 51 microg/km and 371 microg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1- and 0.18-microm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 microm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.     

Is the integration of hormesis and essentiality into ecotoxicology now opening Pandora's Box?

Hormesis and essentiality are likely real and common effects at the level of the individual. However, the widespread incorporation of stimulatory effects into applications of ecotoxicology requires the acceptance of assumptions, value judgements and possibly lowering of water/sediment quality standards. There is also currently little data appropriate for considering hormetic effects in the ecotoxicological context. Except perhaps in the case of fitting concentration-response curves, it is not clear that incorporation of hormetic and essentiality type responses into ecotoxicology is necessary. Furthermore, its incorporation presents considerable intellectual and practical changes for ecotoxicology and could have unanticipated consequences.