An evaluation of a short-term chronic effluent toxicity test using sheepshead minnow (Cyprinodon variegatus) larvae

In response to recent changes in National Pollutant Discharge Elimination System (NPDES) permit regulations, rapid (7-day) static renewal toxicity tests have been developed to detect chronic (sublethal and lethal) effect concentrations of municipal and industrial effluents on freshwater and marine/estuarine organisms. This paper evaluates results from short-term (7-day) chronic effluent tests measuring effects on the growth and survival of the larvae of estuarine sheepshead minnow (Cyprinodon variegatus). Growth was the more sensitive endpoint in 52% of the effluent tests; survival was most sensitive in 7% of the tests. Growth and survival were equally sensitive endpoints in 26% of the tests, while there was no effect on either endpoint at the highest test concentration in 15% of the tests. Four short-term chronic tests were conducted concurrently with early life stage (ELS) tests using a common effluent. Effect concentrations were generally (two of three) within one dilution (a factor of three). Comparison of short-term chronic and ELS tests were also conducted with reference single chemicals and the results were slightly better than the effluent comparisons. A series of ten intralaboratory tests and seven interlaboratory tests were conducted to assess the variability among tests results. Toxicity in these tests varied by no more than one test concentration interval. We concluded that this sheepshead minnow test is suitable to estimate chronic values for complex effluents discharged to marine/estuarine environments within the NPDES permit regulations.     

Reactive oxygen species responsible for the enhanced desorption of dodecane in modified Fenton's systems.

The enhanced treatment of sorbed contaminants has been documented in modified Fenton's reactions; contaminants are desorbed and degraded more rapidly than they desorb by fill-and-draw or gas-purge desorption. The reactive species responsible for this process was investigated using dodecane as a model sorbent. Hydroxyl radical, hydroperoxide anion, and superoxide radical anion were generated separately to evaluate their roles in enhanced dodecane desorption. Dodecane desorption from silica sand over 180 minutes was negligible in gas-purge systems and in the hydroxyl radical and hydroperoxide anion systems. In contrast, enhanced desorption of dodecane occurred in superoxide systems, with >80% desorption over 180 minutes. Scavenging of superoxide eliminated the enhanced desorption of dodecane in both superoxide and modified Fenton's systems, confirming that superoxide is the desorbing agent in modified Fenton's reactions. Conditions that promote superoxide generation in Fenton's reactions may enhance their effectiveness for in situ subsurface remediation of sorbed hydrophobic contaminants.     

Ultraviolet spectrophotometric determination of nitrate: detecting nitrification rates and inhibition.

Simple methods that rapidly detect nitrification inhibition are needed to enforce pretreatment programs and prevent upsets. The objective of this study was to demonstrate a rapid method for measuring nitrification inhibition by using nitrate generation rates (NGRs) coupled with direct UV detection of nitrate. The NGRs were measured with UV spectrophotometry at wavelengths between 225 and 240 nm, without chemical manipulation, and verified against ion chromatography. The method was shown to quickly and accurately measure nitrate concentrations after correcting for nitrite interference. Cadmium, hypochlorite and 1-chloro-2,4-dintrobenzene (CDNB) were tested for their ability to cause nitrification inhibition using this method. The CDNB was found to cause a correctable interference with the test, while hypochlorite provided an uncorrectable interference. Used as a batch method coupled with biotic and abiotic controls, this approach can be deployed at full-scale treatment plants as a relatively rapid (1.5 hours) means of identifying nitrification-inhibiting wastewaters.     

Activated sludge inhibition by chemical stressors--a comprehensive study.

The effects of shock loads of 1-chloro-2,4-dinitrobenzene (CDNB); cadmium; 1-octanol; 2,4-dinitrophenol (DNP); weakly complexed cyanide; pH 5, 9, and 11; and high ammonia levels on activated sludge biomass growth, respiration rate, flocculation, chemical oxygen demand removal, dewaterability, and settleability were studied. For all chemical shocks, except ammonia and pH, concentrations that caused 15, 25, and 50% respiration inhibition were used to provide a single pulse shock to sequencing batch reactor systems containing a nitrifying or non-nitrifying biomass. Cadmium and pH 11 shocks were most detrimental to all processes, followed by CDNB. The DNP and cyanide primarily affected respiration, while pH 5, pH 9, octanol, and ammonia did not affect the treatment process to a significant extent. A chemical source-process effect matrix is provided, which we believe will aid in the development of methods that prevent and/or attenuate the effects of toxic shock loads on activated sludge systems.     

Displacement and sweep efficiencies in a DNAPL recovery test using micellar and polymer solutions injected in a five-spot pattern

Soil washing with micellar solutions is a promising alternative for the remediation of DNAPL source zones. As with any flushing technology, the success of soil washing with micellar solutions depends in a very large part on the ability of the solution to contact the contaminant (sweep efficiency) and then on the efficiency of contaminant removal once this contact is made (displacement efficiency). We report here on a field test where a micellar solution was used to recover a DNAPL in an open five-spot pattern in which polymer solutions were also injected before and after the washing solution to improve sweep efficiency. The washing solution formulation was optimised in the laboratory prior to the test to obtain good dissolution capacity. For a high-concentration and low-volume soil flushing remediation test such as the one performed (0.8 pore volumes of actual washing solution injected), slug sizing of the washing solution is critical. It was evaluated by an analytical solution. In a five-spot pattern, the displacement efficiency of the washing solution was observed to vary in the porous medium as a function of the radial distance from the injection well because: (1) the volume of the washing solution flowing through a section of the test cell changes (maximum close to the injection well and minimal at the pumping wells); (2) the in situ velocity changes (maximum at the wells and minimum between the wells) and; (3) the contact time of the washing solution with the NAPL changes as a function of the distance from the injection well. The relative importance of the recovery mechanisms, mobilisation and dissolution, was also observed to vary in the test cell. The reduced velocity increased the contact time of the washing solution with the DNAPL enhancing its dissolution, but the decrease of the capillary number caused less mobilisation. The washing process is much more extensive around the injection well. The use of an injection-pumping pattern allowing a complete sweep of the remediated area is essential. Following a comprehensive characterisation, modeling is an efficient tool to design the injection-pumping scheme and to optimise injection and pumping rates providing the best areal sweep. The vertical sweep can be controlled by using a polymer solution (Xanthan gum). The polymer solution also has a positive effect on front stability between the solutions injected. The injection rate of the polymer solution that follows the washing solution must be kept minimal initially to prevent dilution of the washing solution by fingering.     

Dissipation of oxytetracycline, chlortetracycline, tetracycline and doxycycline using HPLC-UV and LC/MS/MS under aquatic semi-field microcosm conditions

A mixture of four tetracyclines; oxytetracycline (OTC), chlortetracycline (CTC), tetracycline (TC), and doxycycline (DC) was applied in fifteen 12000l outdoor microcosms at four treatment levels plus controls each with three replicates (n = 3). The dissipation times of parent compounds were monitored and half-lives (DT50) of 1-4 days, depending on treatment level were recorded. This is in accordance with half-lives from previous findings in bench-top experiments. Parent compound DT50, were determined using HPLC-UV. Furthermore, the samples were analyzed for ten different tetracycline products using LC/MS/MS. Two products were found for chlortetracycline; 4-epi-anh-chlortetracyline and the iso-chlortetracycline. Iso-forms were only found for CTC and only at the highest treatment (300 microg l(-1)). The half-lives, trajectories, and relative amounts of the products were analogous for all four tetracyclines. DT50 for products were less than 1.2 days. Formation of 4-epi-anh-tetracyclines, occurred at neutral to weak alkaline conditions.     

A constant-volume rapid exhaust dilution system for motor vehicle particulate matter number and mass measurements

An improved version of the constant volume sampling (CVS) methodology that overcomes a number of obstacles that exist with the current CVS dilution tunnel system used in most diesel and gasoline vehicle emissions test facilities is presented. The key feature of the new sampling system is the introduction of dilution air immediately at the vehicle tailpipe. In the present implementation, this is done concentrically through a cylindrical air filter. Elimination of the transfer hose conventionally used to connect the tailpipe to the dilution tunnel significantly reduces the hydrocarbon and particulate matter (PM) storage release artifacts that can lead to wildly incorrect particle number counts and to erroneous filter-collected PM mass. It provides accurate representations of particle size distributions for diesel vehicles by avoiding the particle coagulation that occurs in the transfer hose. Furthermore, it removes the variable delay time that otherwise exists between the time that emissions exit the tailpipe and when they are detected in the dilution tunnel. The performance of the improved CVS system is examined with respect to diesel, gasoline, and compressed natural gas vehicles.     

Holocene biomass burning and global dynamics of the carbon cycle

Fire regimes have changed during the Holocene due to changes in climate, vegetation, and in human practices. Here, we hypothesise that changes in fire regime may have affected the global CO2 concentration in the atmosphere through the Holocene. Our data are based on quantitative reconstructions of biomass burning deduced from stratified charcoal records from Europe, and South-, Central- and North America, and Oceania to test the fire-carbon release hypothesis. In Europe the significant increase of fire activity is dated approximately 6000 cal. yr ago. In north-eastern North America burning activity was greatest before 7500 years ago, very low between 7500-3000 years, and has been increasing since 3000 years ago. In tropical America, the pattern is more complex and apparently latitudinally zonal. Maximum burning occurred in the southern Amazon basin and in Central America during the middle Holocene, and during the last 2000 years in the northern Amazon basin. In Oceania, biomass burning has decreased since a maximum 5000 years ago. Biomass burning has broadly increased in the Northern and Southern hemispheres throughout the second half of the Holocene associated with changes in climate and human practices. Global fire indices parallel the increase of atmospheric CO2 concentration recorded in Antarctic ice cores. Future issues on carbon dynamics relatively to biomass burning are discussed to improve the quantitative reconstructions.     

Comparison of photochemical behavior of various humic substances in water: II. Photosensitized oxygenations

The photochemical oxygenation of 2,5-dimethylfuran (DMF) in water was studied under a variety of reaction conditions employing various humic substances as photosensitizers. As predicted by theory, the reactions at low DMF concentrations were first order with respect to DMF, and the reaction rate constants were directly proportional to the average light intensity and to the concentration of humic substance. The rate of oxygenation photosensitized by the humic matter from a river was independent of hydrogen ion activity in the pH 5 to 9 range. Wavelength studies indicate that oxygenations photosensitized by humic substances are induced by ultraviolet and blue radiation. Rate constants computed for this photosensitized reaction in sunlight were in close agreement with experimental values. Calculations also show that the ratio of the sunlight rate constants to total visible solar irradiance (400 to 700 nm) is approximately constant. Therefore, it may be possible to calibrate rate constants for photosensitized reactions in terms of commonly measured units of visible light intensity such as foot candles.     

Tracking the anthropogenic drivers of ecological impacts

Despite the pivotal role human factors (anthropogenic drivers) are presumed to play in global environmental change, substantial uncertainties and contradictory conclusions about them continue. We attempt to further discipline the human factors issue by estimating the effects of two anthropogenic drivers, population and affluence, on a wide variety of global environmental impacts, including greenhouse gas emissions, emissions of ozone depleting substances, and the ecological footprint. Population proportionately increases all types of impacts examined. Affluence typically increases impacts, but the specific effect depends on the type of impact. These findings refocus attention on population and material affluence as principal threats to sustainability and challenge predictions of an ameliorating effect of rising affluence on impacts.