Determination of metoxuron and 3-chloro-4-methoxyaniline via direct derivatization with heptafluorobutyric anhydride and GC-ECD

The phenylurea herbicide metoxuron and its main metabolite, 3-chloro-4-methoxyaniline, can be determined rapidly in aqueous samples via extraction, derivatization with heptafluorobutyric anhydride (HFBA), washing with an aqueous bufferof pH 8, and analysis by capillary GC with electron capture detection. Linear calibration curves are obtained over two orders of magnitude, and the detection limit for the HFB derivatives is about 0.5 pg. The method has successfully been applied to several types of water samples.     

Effects of an industrial effluent on plant colonization and on the germination and post-germinative growth of seeds of terrestrial and aquatic plant species

Major oil sands industrial companies are located in the Athabasca Oil Sands Deposit in northeastern Alberta, Canada. During the process used to extract light crude oil (via hot water digestion and flotation), gypsum is usually added to produce consolidated tails (CT) and CT release water. The vast volumes of process-treated waters (effluent) are held within large dyked tailings ponds. Toward testing viable options for reclamation, various hummock-wetlands systems have been constructed; in addition, natural wetlands (inhabited by obligate wetland plant species) have become established as a result of seeping of the effluents held within the large dyked ponds. Vegetation surveys conducted on and around the industrial site revealed that the constructed wetlands associated with the dyke drainage (effluent treated with phosphorous) and consolidated tails (CT; effluent treated with gypsum) had low biodiversity and were not invaded by many aquatic plants. Although the natural wetland was also not invaded by many aquatic species, it was found to be as diverse as the reference wetlands (i.e. off-site wetlands not exposed to the effluents). Exposure to oil sands effluents had an inhibitory effect on the germination (percent and/or rate) of several plant species (tomato, clover, wheat, rye, pea, reed canary grass, loblolly pine); clover and tomato seed germination were most affected. Two treatments in particular (effluents from the natural on-site wetland and the CT constructed wetland), delayed germination, and also led to reduced fresh weight of seedlings of tomato, wheat, clover and loblolly pine. The osmolarities of the effluents associated with the natural on-site wetland and CT constructed wetland were 712 and 728 mOs/kg, respectively; substituting these effluents with solutions of polyethylene glycol of the same osmotic potentials had a greater inhibitory effect on germination rate. The negative effects of the effluents on seed germination may account for the paucity of aquatic species that invaded the oil sands impacted wetlands. This factor will also be critical in determining the long-term feasibility of hummock-wetland systems.     

Analysis of the long-term behavior of solute transport with nonlinear equilibrium sorption using breakthrough curves and temporal moments

We analyzed the long-term behavior of breakthrough curves (BTCs) and temporal moments of a solute subjected to Freundlich equilibrium sorption (s = kc(n)). For one-dimensional transport in a homogeneous porous medium, we derived a power-law relation between travel time, tau, and solute displacement, chi, with the exponent being equal to the Freundlich n exponent. The mean solute velocity, derived from the first time moment, was found to change as tau(n-1). For n values larger than 0.66, the second time moment could be related to c chi(2/n), where c is a constant. An approach based on the use of a critical concentration was developed to estimate the presence of the asymptotic regime in the tail of the BTC. This approach was tested successfully using numerical case studies. One-dimensional numerical simulations with varying values of k, n and initial mass were run to verify the closed form analytical expressions for the large time behavior of temporal moments and the tailing part of breakthrough curves. Good agreement between the slope of the tailing part of log-log transformed BTCs and the predicted slope using asymptotic theory was found. Asymptotic theory in general underestimated the magnitude of the concentration in the tail. The quality of the estimated concentrations in the tail improved for small values of the dispersivity. Experimental BTCs of uranin and benazolin were analyzed in combination with sorption/desorption batch experiments using asymptotic theory. A good agreement between the value of n parameter derived from desorption experiment with benazolin and the value of the n parameter derived from the tail of the BTC was found.     

Oxidant stress, antioxidants and nitric oxide in traffic police of Hyderabad, India

Exposure to environmental pollutants is known to be harmful to health, in general, and to lungs in particular. In this respect, traffic police are at particular risk due to the nature of their job, since they are exposed to emissions from the vehicles. Here, we show that in the traffic police of Hyderabad city, India, the plasma levels of lipid peroxides are high, whereas the concentrations of the nitric oxide are low. In addition, the levels of various antioxidants in the RBC lysate such as catalase, superoxide dismutase and glutathione peroxidase were found to be low with no significant alteration in plasma ceruloplasmin levels. These results suggest that exposure to air pollutants, a major portion of which is due to emissions from the vehicles, can increase oxidant stress, decrease the levels of antioxidants and nitric oxide. This imbalance in the oxidant/antioxidant system may lead to lung damage and is likely to cause respiratory problems in individuals exposed to air pollution.     

Levels of PCB 126 and PCB 153 in plasma and tissues in goats exposed during gestation and lactation

The aim of the present study was to gain knowledge about the disposition of the PCB congeners 126 and 153 in a goat model where pregnant does were given oral doses of PCB from day 60 of gestation until delivery. The goat kids were thus exposed to PCB during gestation and lactation. The doses of PCB 153 and PCB 126 were 98 and 49 ng/kg body wt/day, respectively. PCB levels were measured in plasma from the does at day 90 of gestation and at delivery, and in plasma from the kids at birth and four weeks post partum. Concentrations of PCB were analysed in brain, liver and fat tissue from the does six weeks after delivery and in liver and fat tissue from the kids at nine months of age. The ratio of estimated body burden to ingested dose in the does, was 0.95 +/- 0.07 for PCB 153 and 0.41 +/- 0.03 for PCB 126. Approximately 9% of PCB 153 and 6% of PCB 126 was transferred from the mothers to their kids during gestation and lactation. Prenatal exposure contributed to a much lower fraction of the body burden than postnatal PCB intake via milk, due to the fact that almost 100% of the PCB 153 transferred from the does to kids was transferred via milk, and the PCB 126 intake via milk was threefold higher than the calculated body burden. The hepatic PCB 126 concentration in both does and kids was significantly higher than the concentration in fat, in contrast to PCB 153, where the highest concentrations were found in fat. A significant difference in body burden between the does at delivery, the newborn kids, and the kids at four weeks of age, did not influence the plasma concentration of PCB 153 on a fat weight basis, which showed no difference with sampling time. Our results suggest that PCB 126 and PCB 153 have different pharmacokinetic properties. The higher levels of PCB 126 in liver tissue compared to fat tissue confirm the concept of hepatic sequestration. The similar blood concentration of PCB 153 in the does at delivery and their newborn kids despite the considerable difference in body burden, suggests a high degree of placental transfer. This supports previous observations that low molecular weight, lipid-soluble, non-polar chemicals reach the fetus to the greatest possible extent. For PCB 153, the body burden may provide the appropriate dose metric at steady state, but may give a minor underestimation of PCB 126 at low environmental exposure levels due to hepatic sequestration.     

Toxicity and bioaccumulation of thallium in Hyalella azteca, with comparison to other metals and prediction of environmental impact

Thallium (Tl) is an extremely toxic but little studied metal. For Hyalella azteca exposed in Lake Ontario water, a 25% reduction in survival (the LC25) occurred at about 48 nmol litre(-1) after 4 weeks. Body concentrations of Tl, which were proportional to water concentrations, averaged 290 nmol g(-1) dry mass at the LC25. Growth was reduced at slightly lower concentrations. Concentrations affecting reproduction were variable at < 50% of the LC25. On a water-concentration basis Tl was more toxic than Ni, Cu or Zn, but less toxic than Cd or Hg to Hyalella; toxicity to Pb was similar. On a body-concentration basis, the toxicities of Tl, Cd, Hg and Pb were all similar. Unlike Cd, Tl toxicity and uptake was affected by K concentrations in the water, and not by Ca, Mg, Na or other ions. Toxicity was proportional to uptake, and body concentrations were better predictors of toxicity than water concentrations in media with varying K concentrations. Preliminary measurements of Tl and Cd uptake by Hyalella from Hamilton Harbour and Lake Ontario sediments suggested that total bioavailable metal concentrations were greater in deep-water sediments from Lake Ontario than in sediments from the harbour. The ratio of bioavailable metal to the toxic threshold was slightly higher for Cd than for Tl, but well below 1 for both metals.     

Levels of polychlorinated biphenyls, organochlorine pesticides, mercury, cadmium, copper, selenium, arsenic, and zinc in the harbour seal, Phoca vitulina, in Norwegian waters

Residue levels of the chlorinated hydrocarbons polychlorinated biphenyls (PCBs), total DDT, alpha-, beta- and gamma-hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), and oxychlordane in blubber, and the elements mercury, cadmium, copper, selenium, arsenic, and zinc in liver, of 82 harbour seals, Phoca vitulina, were determined. The seals were found dead or dying in Norwegian waters during the disease outbreak caused by a morbilli virus in 1988. Of the chlorinated hydrocarbons, the highest concentrations were found of PCBs, which were 2-4 times higher than the total DDT concentrations. P,p'-DDE was the main contributor to the total DDT, and constituted about 80%. The PCB and total DDT concentrations ranged from 0.4-38 and 0.1-8.8 mg kg(-1), respectively. The mercury concentrations ranged from 0.1-89 mg kg(-1). Significantly higher mean levels of PCBs (13 mg kg(-1) and mercury (16 mg kg(-1)) were found in blubber and liver, respectively, of seals from the Southern coast of Norway, as compared to the corresponding mean levels in seals from the Oslofjord (8.8 and 4.1 mg kg(-1)), and at the Northwestern coast (5.8 and 7.9 mg kg(-1)), respectively. A significant positive correlation was found between the concentrations of selenium and mercury. When the seals were grouped according to sex and age, females of ageclass > 1 and pups of both sexes had significantly lower PCB and total DDT levels than males ageclass > 1. Significantly higher hepatic mercury levels were found in seals ageclass > 1 as compared to pups. Only low levels of the other organochlorines, cadmium and arsenic, were found. Copper and zinc were considered to be present at normal physiological levels. The present organochlorine and heavy metal concentrations gave no support to suggestions that organochlorines and heavy metal pollution may be directly involved in the observed seal deaths.