Reducing atrazine losses: water quality implications of alternative runoff control practices

Water quality is being affected by herbicides, some allegedly harmful to human health. Under scrutiny is atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), a commonly used herbicide in corn (Zea mays L.) and sorghum [Sorghum bicolor (L.) Moench] production. Concentrations of soluble and adsorbed atrazine losses sometimes exceed the safe drinking water standard of 3 microg L(-1) established by the USEPA. This study assesses the protective implications of runoff control structures and alternative crop farming practices to minimize atrazine losses. Using a computerized simulation model, APEX, the following four practices were the most effective with respect to the average atrazine loss as a percent of the amount applied: (i) constructing sediment ponds, 0.09%; (ii) establishing grass filter strips, 0.14%; (iii) banding a 25% rate of atrazine, 0.40%; and (iv) constructing wetlands, 0.45%. Other atrazine runoff management options, including adoption of alternative tillage practices such as conservation and no-till as well as splitting applications between fall and spring, were marginally effective.     

Influence of organic loading on an anaerobic sequencing biofilm batch reactor (ASBBR) as a function of cycle period and wastewater concentration

The effect of organic loading on the performance of a mechanically stirred anaerobic sequencing biofilm batch reactor (ASBBR) has been investigated, by varying influent concentration and cycle period. For microbial immobilization 1-cm polyurethane foam cubes were used. An agitation rate of 500 rpm and temperature of 30+/-2 degrees C were employed. Organic loading rates (OLR) of 1.5-6.0gCODl(-1)d(-1) were applied to the 6.3-l reactor treating 2.0 l synthetic wastewater in 8 and 12-h batches and at concentrations of 500-2000mgCODl(-1), making it possible to analyze the effect of these two operation variables for the same organic loading range. Microbial immobilization on inert support maintained approximately 60 gTVS in the reactor. Filtered sample organic COD removal efficiencies ranged from 73 to 88% for organic loading up to 5.4gCODl(-1)d(-1). For higher organic loading (influent concentration of 2000mgCODl(-1) and 8-h cycle) the system presented total volatile acids accumulation, which reduced organics removal efficiency down to 55%. In this way, ASBBR with immobilized biomass was shown to be efficient for organic removal at organic loading rates of up to 5.4gCODl(-1)d(-1) and to be more stable to organic loading variations for 12-h cycles. This reactor might be an alternative to intermittent systems as it possesses greater operational flexibility. It might also be an alternative to batch systems suspended with microorganisms since it eliminates both the uncertainties regarding granulation and the time necessary for biomass sedimentation, hence reducing the total cycle period.     

Quantifying the global fractionation of polychlorinated biphenyls

Due to the wide range of their physical-chemical properties, polychlorinated biphenyls (PCBs) have played an important role in the derivation of the global fractionation hypothesis, which predicts changes in the composition of persistent organic pollutant mixtures with latitude. Recent historical emission estimates, the derivation of an internally consistent property data set, in combination with a zonally averaged global fate and transport model, allow a quantitative investigation of the compositional shifts PCBs experience as a function of environmental compartment, latitude and time. Model simulations reproduce the higher relative abundance of lighter PCB congeners with increasing latitude, observed in air and soil, and quantify the relative importance of partitioning, persistence and emissions in establishing PCB patterns. Compositional variations consistent with global fractionation, as well as inverted concentration profiles with higher levels in the Arctic than at lower latitudes, are consistent with only minor fractions of the global PCB inventory being transferred northward.     

Integrative Evaluation of the Ecological Quality of Metalliferous Streams (Chalkidiki, Macedonia, Hellas)

The present study reports on a year-long (November 1997-November 1998) study of water quality in streams of the Olympias and Skouries areas of Chalkidiki (Hellas), subject to past and present mining activities. Benthic macroinvertebrates were collected from 18 sampling sites at five sampling intervals, while several physicochemical parameters of the water (D.O., pH, temperature, nutrients etc.) were also measured. Five European biotic indices and scores and two multivariate statistical methods (CANOCO, FUZZY) were applied to the macroinvertebrate data. The concentration of various trace metals in the water, sediment, fish and crustaceans were also measured. Most sampling stations exhibited a highly diverse macroinvertebrate fauna during the whole year. However, a slight amelioration of water quality was observed during the high-flow period (winter and early spring), regarding diversity of several invertebrate groups, especially pollution-sensitive families, which decreased. The European biotic indices and scores proved to be relatively ineffective in describing water quality and it is suggested that an Hellenic biotic indice or score should be created. The bioaccumulation studies indicated variable effects of trace metals and organic load on macroinvertebrates according to the degree of load.     

MTBE oxidation byproducts from the treatment of surface waters by ozonation and UV-ozonation

In recent years, there has been considerable concern over the release of methyl tert-butyl ether (MTBE), a gasoline additive, into the aquifers used as potable water sources. MTBE readily dissolves in water and has entered the environment via gasoline spills and leaking storage tanks. In this paper, we investigate ozonation and UV-ozonation for treatment of MTBE in contaminated drinking water sources. We report the test protocol and results of using solid-phase microextraction (SPME) to determine the level of MTBE and its oxidation byproducts in samples drawn from laboratory-scale ozone and UV-ozone reactors being evaluated at a US EPA research facility. Analysis of a prepared MTBE standard indicated a detection limit on the order of 0.1 microgl(-1) with a repeatability of +/-0.4%. Results show that the overall rate of removal of MTBE via UV-ozonation in a relatively turbid surface water (15 ntu) is twice that of ozonation alone. In addition, GC-MS analysis of decomposition products showed that tert-butyl formate (TBF), methyl acetate, butene, acetone, and acetaldehyde were produced by both processes. TBF and butene reach similar maximum yields from the two processes, but are more efficiently degraded by UV-ozonation treatment. This indicates that these treatment processes also degrade these byproducts. In contrast, the remaining byproducts (methyl acetate, acetone, and acetaldehyde) are formed at similar levels during treatment, but are not degraded once formed. These byproducts may be resistant to hydrogen abstraction by hydroxyl radical.     

Development and validation of a method for analysis of "dioxin-like" PCBs in environmental samples from the steel industry

A method, previously used for determination of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), has been modified for quantitative analysis of "dioxin-like" polychlorobiphenyls (PCBs) in environmental samples from the steel industry. The existing sample clean-up procedure, involving liquid chromatography on multi-layered silica and Florisil columns, has been extended to include a third chromatography stage on a basic alumina stationary phase. The additional clean-up stage is required for PCB analysis in order to eliminate interferences from relatively large concentrations of saturated cyclic and aliphatic hydrocarbons. Samples were analysed for WHO-12 congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) and standard solutions of the method US EPA 1668A. Replicate analysis of method blanks revealed background contamination for PCBs 118, 105 and 77, which are generally abundant in ambient air. These contaminants were taken into account using a subtraction method. The entire procedure was validated by replicate analysis (N = 3) of a certified reference sediment. The RSD for each WHO-12 congener was below 15%, 13C12-labelled PCB internal standard recoveries were in the range 70-95%. A waste dust sample collected in the electrostatic precipitator of a UK sinter plant was analysed for determination of PCDD/Fs and WHO-12 PCBs and exhibited a PCDD/F I-TEQ of 148.5 +/- 21.2 ngkg(-1) and a WHO-TEQ of 7.2 +/- 1.5 ngkg(-1). WHO-12 congeners contributed only 4.6% to the overall TEQ and PCB 126 was the major congener contributing to the WHO-TEQ (96%). The contribution to the overall TEQ of the waste dust sample was mainly attributed to PCDF followed by PCDD, which accounted for 86.6% and 8.7% to the overall TEQ, respectively.     

Acute and chronic effects of clofibrate and clofibric acid on the enzymes acetylcholinesterase, lactate dehydrogenase and catalase of the mosquitofish, Gambusia holbrooki

The objective of this study was to investigate both acute and chronic effects of clofibrate and clofibric acid on the enzymes acetylcholinesterase (AChE), lactate dehydrogenase (LDH) and catalase (CAT) of the mosquitofish (Gambusia holbrooki). AChE, commonly used as a biomarker of neurotoxicity, was determined in the total head. LDH, an important enzyme of anaerobic metabolism, was quantified in dorsal muscle, and CAT, enzyme which has been used as indicative parameter of peroxisome proliferation, was determined in the liver. Furthermore, alterations of body and liver weight were also determined, through the calculation of the ratios final body weight/initial body weight, liver weight/final body weight, liver weight/gills weight and liver weight/head weight. Acute exposure of G. holbrooki to both clofibrate and clofibric acid induced a decrease in liver CAT activity, an increase in muscle LDH activity, while no effects were observed on AChE activity. However, chronic exposure did not alter significantly the enzymatic activities, suggesting reduced or null effects over these pathways, relative to effects reported in other species. No effects were observed for the calculated ratios, except a significant weight reduction for males chronically exposed to clofibrate.     

Adsorption of bentazon and propanil from aqueous solutions at the high area activated carbon-cloth

Removal of the pesticides bentazon and propanil from single and bisolute solutions by adsorption at the high area activated carbon-cloth was investigated. Kinetics of adsorption was followed and adsorption isotherms of the two pesticides were determined. A special V-shaped cell with an UV cuvette attached to it was used for adsorption studies. With this cell it was possible to follow the concentration of pesticide molecule by in situ UV spectroscopy as it is adsorbed at the carbon-cloth. It was found that concentration of pesticides decreased from the same initial concentration of 4.5 x 10(-5) to 1.1 x 10(-5) for bentazon and to 9.5 x 10(-6) for propanil in about 2 h. The fits of experimental adsorption isotherm data to Langmuir and Freundlich isotherm equations were almost equally successful. Monolayer capacities determined from Langmuir isotherms of pesticides showed that bentazon has greater monolayer capacity than propanil. This conclusion was also confirmed through the 1/n parameter of Freundlich equation.     

Monitoring of eutrophication and nutrient limitation in the Izmir Bay (Turkey) before and after Wastewater Treatment Plant

The distribution of inorganic nutrients and phytoplankton chlorophyll-a was investigated and N/P ratios were determined in Izmir Bay during 1996-2001. The average concentrations showed ranges of 0.01-0.19 and 0.01-10 microM for phosphate-phosphorus; 0.11-1.8 and 0.13-27 microM for (nitrate+nitrite)-nitrogen, 0.30-4.1 and 0.50-39 microM for silicate and 0.02-4.3 and 0.10-26 microg l(-1) for chlorophyll-a in the outer and middle-inner bays, respectively. The results are compared with the values obtained from the relatively unpolluted waters of the Aegean Sea. The N/P ratio is significantly lower than the assimilatory optimal (N/P=15:1) in conformity with Redfield's ratio N/P=16:1. Nitrogen is the limiting element in the Izmir Bay. Phosphate, which originates from detergents, is an important source for eutrophication in the bay, especially in the inner bay. In early 2000, a Wastewater Treatment Plant (WTP) began to treat domestic and industrial wastes. This plant treats the wastes about 60% capacity between 2000 and 2001. The sampling periods cover before and after treatment plant. Although the capacity of wastewater plant is sufficient for removal of nitrogen from the wastes, it is inadequate for removal of phosphate. This is also in accordance with the decreasing N/P ratios observed during 2000-2001 (after WTP) in the middle-inner bays.     

Environmental impact of unleaded gasolines in the bay of Cádiz (Spain)

Given the strategic situation of the José León de Carranza bridge, which spans the Bay of Cádiz (in the SW of Spain) and carries very heavy motor traffic, together with knowledge of the currents and tidal flows in the zone, we have used a technique of radioactive dating of sediments to study the temporal evolution presented by contamination from lead in the sediment column. This has allowed us to observe the environmental impact, in terms of the concentration of Pb in the sea bed sediments, that has been produced in the zone by the introduction of unleaded gasolines as substitutes for traditional automobile fuels that employ organic forms of tetra methyl lead as an antidetonant agent in the fuel.