Reductive degradation of carbaryl in water by zero-valent iron

Reduction of carbaryl solution by zero-valent iron powder (ZVIP) was studied in a rotator batch system (70 rpm) in order to evaluate the utility of this reaction in remediation of carbamate contaminated water. Degradation with different amount of ZVIP: 0.01, 0.02, 0.03, 0.04 g/ml at pH 6.6 and at ambient temperature was investigated. The results show that the process exhibits a degradation rate appearing to be directly proportional to the surface contact area of ZVIP (325-mesh) with the carbaryl molecules. Three analytical techniques were used to monitor carbaryl degradation: (1) A UV-Vis diode array spectrophotometer was used to record all spectra. (2) A high performance liquid chromatography was used to separate by-products and examine the evolution of breakdown products. (3) A home-built spectrophosphorimeter that uses the solid surface room temperature phosphorescence (SSRTP) was employed to observe selectively the decline of the carbaryl concentration at different amount of ZVIP on Whatman no. 1 filter paper. Results show that the reducing degradation of carbaryl with ZVIP as the source of electrons is effective with a half-life close to several minutes.     

Volatilisation of triallate as affected by soil texture and air velocity

The rate of volatilisation of the formulated herbicide triallate was investigated in a wind tunnel under controlled wind-speed conditions. An experimental set-up is described which allows the monitoring of wind speed (w.s.), soil-water content, and the temperature of air and soil. A system controlling soil-water content is also described. The influence of air velocity and soil texture was investigated measuring the cumulative volatilisation losses of triallate from soil. The herbicide volatilisation losses after application ranged from 40% at 3 m/s to 53% at 9 m/s for loam soil and from 60% at 3 m/s to 73% at 9 m/s for sandy soil.     

Nutrient losses by surface run-off following the application of organic manures to arable land. 2. Phosphorus

Phosphorus (P) surface run-off losses were studied following organic manure applications to land, utilising a purpose-built facility on a sloping site in Herefordshire under arable tillage. Different rates and timing of cattle slurry, farm yard manure (FYM) and inorganic nitrogen (N) and P fertiliser were compared, over a 4-year period (1993-97). N losses from the same studies are reported in a separate paper. The application of cattle FYM and, especially slurry, to the silty clay loam soil increased both particulate and soluble P loss in surface water flow. Losses via subsurface flow (30 cm interflow) were consistently much lower than via surface water movement and were generally unaffected by treatment. Increased application of slurry solids increased all forms of P loss via surface run-off; the results suggested that a threshold for greatly increased risk of P losses via this route, as for N, occurred at ca. 2.5-3.0 t/ha solids loading. This approximates to the 50 m3/ha application rate limit suggested for slurry within UK 'good agricultural practice'. The studies also provided circumstantial evidence of the sealing of the soil surface by slurry solids as the major mechanism by which polluting surface run-off may occur following slurry application on susceptible soils. Losses of total and soluble P, recorded for each of the 4 years of experiments, reached a maximum of only up to 2 kg/ha total P (TP), even after slurry applications initiating run-off. Whilst these losses are insignificant in agronomic terms, peak concentrations of P (up to 30,000 micrograms/l TP) in surface water during a run-off event, could be of considerable concern in sensitive catchments. Losses of slurry P via surface run-off could make a significant contribution to accelerated eutrophication on entry to enclosed waters, particularly when combined with high concentrations of NO3(-)-N. Restricting slurry application rates to those consistent with good agronomic practice, and within the limits specified in existing guidelines on good agricultural practice, offers the simplest and most effective control measure against this potentially important source of diffuse pollution.     

Lead shot toxicity to passerines

This study evaluated the toxicity of a single size 7.5 lead shot to passerines. No mortalities or signs of plumbism were observed in dosed cowbirds (Molothrus ater) fed a commercial diet, but when given a more natural diet, three of 10 dosed birds died within 1 day. For all survivors from which shot were recovered, all but one excreted the shot within 24 h of dosing, whereas, the dead birds retained their shot. Shot erosion was significantly greater (P < 0.05) when weathered shot were ingested compared to new shot, and the greatest erosion was observed in those birds that died (2.2-9.7%). Blood lead concentrations of birds dosed with new shot were not significantly different (P = 0.14) from those of birds exposed to weathered shot. Liver lead concentrations of birds that died ranged from 71 to 137 ppm, dry weight. Despite the short amount of time the shot was retained, songbirds may absorb sufficient lead to compromise their survival.     

Bioaccumulation of butyltins in Dreissena polymorpha at a confined placement facility in Buffalo, New York

This study involves a site characterization followed by biomonitoring with the zebra mussel, Dreissena polymorpha, at the Times Beach confined placement facility (CPF), located in Buffalo, NY. The contaminant of interest was tributyltin (TBT) and the degradation products dibutyltin (DBT) and monobutyltin (MBT). At study initiation (Day 0) TBT levels in the baseline mussels were 5.86 +/- 0.43 ng Sn/g, DBT levels were 2.25 +/- 0.37 ng Sn/g. No MBT was detected in the Day 0 baseline samples. Caged reference mussels placed back in the Black Rock Channel Lock and retrieved on Days 19 and 34 had TBT, DBT, and MBT levels which did not differ significantly from the Day 0 baseline levels. Mussels placed at the Times Beach CPF had TBT concentrations that were significantly lower at both Days 19 (3.65 +/- 0.90 ng Sn/g) and 34 (3.50 +/- 1.03 ng Sn/g) than the Day 0 baseline analysis (5.86 +/- 0.43 ng Sn/g). The results of this study indicate that butyltins were detected at the CPF site in the sediment (7.33 +/- 5.70 ng Sn/g) but not the water column (not detected at 0.01 microgram/l). In this study the zebra mussel was able to depurate TBT even in the presence of contaminated sediment. TBT may be bioaccumulated from the sediments. However, the initial levels in the mussels were so high, levels actually dropped as sediment-tissue equilibria levels were reached by the mussels.     

Air pollution modeling for an industrial complex and model performance evaluation

Jamshedpur, the steel city of India situated in the eastern part of India is affected by increasing air pollution levels as a result of concentrated industrial activities. The impact of NOx emissions resulting from various air pollution sources, viz. industries, vehicles and domestic, was estimated using Industrial Source Complex Short-Term gaussian dispersion model. The contribution of NOx concentration from industrial, vehicular and domestic sources was found to be 53, 40 and 7%. Further statistical analysis was carried out to evaluate the model performance by comparing measured and predicted NOx concentrations. The model performance was found good with an accuracy of about 68%.     

A procedure for use in estimating human exposure to particulate matter of ambient origin

Modern epidemiology has shown that fluctuations of mortality data are statistically significantly correlated with fluctuations of ambient particulate matter (PM) concentration data. This relation cannot be confounded by exposure to PM of indoor origin because the concentrations of ambient PM are not correlated with concentrations of PM of indoor origin. It has been suggested, given the above understanding, that modern PM exposure measurements and analysis should create separate estimates of exposure to all PM of ambient origin and exposure to all PM of nonambient origin (primarily of indoor origin), and not exposure to total PM. This paper reviews the developments of the form of the general microenvironmental mass balance equation that can be utilized for estimating human exposure to PM of ambient origin and for estimating the portion of total PM exposure that is attributable to nonambient origin PM. The equation is perfectly general and can be applied to conditions of time-varying factors that influence exposure, such as rapidly changing air-exchange rates in a home as doors and windows are opened and closed, and turning on and off air cleaners in a home. It is suggested that this procedure be applied in exposure assessment studies and validated using independent techniques of estimating exposure to PM of ambient origin available in the literature.     

On-line real-time measurements at incineration plants: PAHs and a PCDD/F surrogate compound at stationary combustion conditions and during transient emission puffs

Laser mass spectrometry has been applied for on-line monitoring of traces of aromatic compounds from flue gas of incineration plants. The experiments have been carried out at two sampling sites in an industrial hazardous-waste incinerator. With laser mass spectrometry resonance-enhanced multiphoton ionization (REMPI) with time-of-flight mass spectrometry (TOFMS) (REMPI-TOFMS), using the group selective multi-component monitoring approach, aromatic compounds are selectively ionized from the complex flue-gas matrix. In this case, the result of an REMPI-TOFMS on-line measurement is a distinct pattern of aromatic compounds. These patterns are dependent on: (i) the point of measurement, (ii) the incineration plant, (iii) the temperature, and (iv) the fuel. This contribution focuses on the fuel dependence of the pattern. The most transient behavior can be observed when containers filled with hazardous waste are burnt, leading to puffs. Real-time monitoring results of puffs are given. Furthermore, as an approach towards on-line monitoring of the TEQ (PCDD/F toxicity equivalent), REMPI-TOFMS on-line analysis results of chlorobenzene are presented.     

Organic reactions without organic solvents and oils and fats as renewable raw materials for the chemical industry

The use of organic solvents should be minimized as far as possible to reduce atmospheric volatile organic compounds (VOCs). Examples of solvent-free organic syntheses are described. The increasing usage of renewable feedstocks taking advantage of the synthetic potential of nature is another way to avoid organic solvents. Most important is the development of chemical products, i.e., coatings that can be processed without organic solvents.