Organochlorine contamination in bird's eggs from the Danube Delta

In this study we report the levels of organochlorine compounds in eggs of aquatic birds from the Danube Delta, a major European wetland. The eggs were collected in 1997 and belonged to the following species: the mallard (Anas platyrhynchos), the greylag goose (Anser anser), the mute swan (Cygnus olor), the coot (Fulica atra), the glossy ibis (Plegadis falcinellus), the spoonbill (Platalea leucorodia), the little egret (Egretta garzetta), the night heron (Nycticorax nycticorax), the grey heron (Ardea cinerea), the great white egret (Egretta alba), the red-necked grebe (Podiceps griseus), the Dalmatian pelican (Pelecanus crispus), the Pygmy cormorant (Phalacrocorax pygmaeus) and the common cormorant (Phalacrocorax carbo). Dichlorodiphenyltrichloroethane (DDT) levels were higher in eggs of the little egret, the great white egret, the cormorant and the Pygmy cormorant with respect to the other species (48,399, 13,613, 12,400 and 10,417 ng/g dry wt., respectively). Hexachlorobenzene (HCB) levels were lower than 1393 ng/g dry wt. in all species while polychlorinated biphenyl (PCB) concentrations in the Pygmy cormorant (2565 ng/g dry wt.) were higher than in the other species. The toxicity evaluation was based on 2,3,7,8-TCDD toxic equivalent factors (TEF) and non-ortho PCB congeners contributed much more than mono-ortho PCBs in most of species. A further aim of this study was to evaluate the possible differences of organochlorine levels in bird eggs collected in the same area in 1982 and in 1997; generally speaking the levels detected in the latter period were lower than those detected in the earlier one.     

Acute and chronic impacts caused by aromatic hydrocarbons on bacterial communities at Boa Viagem and Forte do Rio Branco Beaches, Guanabara Bay, Brazil

The bacterial community presented significantly different hydrocarbonoclastic activity under acute and chronic impacts. Benzoic acid, toluene, benzene and xylene were used in final concentrations of 5, 10 and 15 mM and bacterial biomass was quantified through protein dosage. Under acute impact, the highest biomass percentages occurred between the 11th and 14th days; under chronic impact, between the 20th and 29th days. Under acute and chronic impacts, the bacterial biomass presented higher nutritional specialization at Boa Viagem Beach, using the aromatic hydrocarbons up to a concentration of 15 mM. Under acute impact, the concentration of the hydrocarbons constituted a critical factor for the bacterial flora from Forte do Rio Beach, because biomass increases only occurred in concentrations of 5 mM; under chronic impact, the aromatic hydrocarbons induced the specialization and increased bacterial biomass for 15 mM toluene. Benzoic acid (15 mM) was used by the bacteria from Boa Viagem and Forte do Rio Branco Beaches.     

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.     

Seedling insensitivity to ozone for three conifer species native to Great Smoky Mountains National Park

Field symptoms typical of ozone injury have been observed on several conifer species in Great Smoky Mountains National Park, and tropospheric ozone levels in the Park can be high, suggesting that ozone may be causing growth impairment of these plants. The objective of this research was to test the ozone sensitivity of selected conifer species under controlled exposure conditions. Seedlings of three species of conifers, Table Mountain pine (Pinus pungens), Virginia pine (Pinus virginiana), and eastern hemlock (Tsuga canadensis), were exposed to various levels of ozone in open-top chambers for one to three seasons in Great Smoky Mountains National Park in Tennessee, USA. A combination of episodic profiles (1988) and modified ambient exposure regimes (1989-92) were used. Episodic profiles simulated an average 7-day period from a monitoring station in the Park. Treatments used in 1988 were: charcoal-filtered (CF), 1.0x ambient, 2.0x ambient, and ambient air-no chamber (AA). In 1989 a 1.5x ambient treatment was added, and in 1990, additional chambers were made available, allowing a 0.5x ambient treatment to be added. Height, diameter, and foliar injury were measured most years. Exposures were 3 years for Table Mountain pine (1988-90), 3 years for hemlock (1989-91), and 1 and 2 years for three different sets of Virginia pine (1990, 1990-91, and 1992). There were no significant (p<0.05) effects of ozone on any biomass fraction for any of the species, except for older needles in Table Mountain and Virginia pine, which decreased with ozone exposure. There were also no changes in biomass allocation patterns among species due to ozone exposure, except for Virginia pine in 1990, which showed an increase in the root:shoot ratio. There was foliar injury (chlorotic mottling) in the higher two treatments (1.0x and 2.0x for Table Mountain and 2.0x for Virginia pine), but high plant-to-plant variability obscured formal statistical significance in many cases. We conclude, at least for growth in the short-term, that seedlings of these three conifer species are insensitive to ambient and elevated levels of ozone, and that current levels of ozone in the Park are probably having minimal impacts on these particular species.     

Trace elements, organochlorines, polycyclic aromatic hydrocarbons, dioxins, and furans in lesser scaup wintering on the Indiana Harbor Canal

During the winter of 1993-94, male lesser scaup (Aythya affinis) were collected on the heavily polluted Indiana Harbor Canal (IHC), East Chicago, IN, USA, and examined for tissue contaminant levels. Lesser scaup collected on the IHC had higher concentrations of cadmium (Cd), mercury (Hg), selenium (Se), polychlorinated biphenyls (PCBs), selected organchlorine pesticides, polychlorinated dibenzodioxins, polychlorinated dibenzofurans, polycyclic aromatic hydrocarbons, and aliphatic hydrocarbons than reference birds. Of the scaup collected on the IHC, 44% had Cd concentrations in the liver considered above background for freshwater waterfowl (>3 microg/g dry wt.), 50% had Se concentrations in the liver above a level possibly harmful to the health of young and adult birds (>33 microg/g dry wt.), and 88% of the scaup carcasses exceeded the PCB human consumption guidelines for edible poultry in the USA (>3.0 microg/g lipid wt.). The ratio of pristane:n-heptadecane concentrations in 47% of lesser scaup collected on IHC was elevated above 1.0, which is indicative of chronic exposure to petroleum hydrocarbons.     

Genotoxicity of two novel pesticides for the earthworm, Eisenia fetida

In this paper, several studies were conducted to evaluate the genotoxicity of two pesticides, Imidacloprid and RH-5849, for earthworm (Eisenia fetida). Earthworms were exposed in different exposure systems to evaluate their acute toxicity and the genotoxicity of the two pesticides was evaluated by using the method of sperm deformity assessment, micronucleus test of root tip cells in Vicia faba, a mouse bone-marrow micronucleus test, and comet assay. LC(50) (interpolated concentration at which 50% mortality of test population occurs) for earthworms varied in different exposure systems. The results indicated that Imidacloprid was consistently more toxic than RH-5849 in all exposure systems. In this study, sperm deformity test was used to detect the potential adverse influences of pesticides on the reproduction of earthworms. The results demonstrated that significant induction of sperm deformity (p<0.01) and a dose-effect relationship displayed at Imidacloprid concentrations higher than 0.5 mg/kg dry soil. However, the sperm deformity frequency of groups exposed to RH-5849 did not show significant difference (p>0.05) from the control until the dose reached 100 mg/kg dry soil. The results of the V. faba micronucleus tests showed that micronuclei frequency of the exposed group did not show significant difference (p>0.05) from the control until the concentration of Imidacloprid and RH-5849 reached 100 mg/ml. The results of the mouse bone-marrow micronuclei test also indicate that two pesticides did not show significant effects (p>0.05) on the micronuclei frequency in mice bone-marrow cells until the dose reached 100 mg/kg for Imidacloprid and 300 mg/kg for RH-5849 (2/3 LD(50)). Although no genotoxicity was detected by using the micronucleus tests, the results of the comet assay showed that the two pesticides induce significant DNA damage (p<0.01) in earthworms and dose-effect relationships were displayed. The 'earthworm comet assay' is a rapid and sensitive way to screen chemicals or terrestrial environments for their DNA-damaging properties.     

In situ sequential treatment of a mixed contaminant plume

Groundwater plumes often contain a mixture of contaminants that cannot easily be remediated in situ using a single technology. The purpose of this research was to evaluate an in situ treatment sequence for the control of a mixed organic plume (chlorinated ethenes and petroleum hydrocarbons) within a Funnel-and-Gate. A shallow plume located in the unconfined aquifer at Alameda Point, CA, was found to contain up to 218,000 μg/l of cis-1,2 dichloroethene (cDCE), 16,000 μg/l of vinyl chloride (VC) and <1000 μg/l of 1,1 dichloroethene (1,1 DCE), trans-1,2 dichloroethene (trans-1,2 DCE) and trichloroethene (TCE). Total benzene, toluene, ethylbenzene and xylenes (BTEX) concentrations were <10,000 μg/l. Contaminated groundwater was funneled into a gate, 3.0 m wide, 4.5 m long and 6.0 m deep (keyed into the underlying aquitard) where treatment occurred. The initial gate segment consisted of granular iron, for the reductive dechlorination of the higher chlorinated ethenes. The second segment, the biosparge zone, promoted aerobic biodegradation of petroleum hydrocarbons and any remaining lesser-chlorinated compounds, stimulated by dissolved oxygen (DO) and carbon dioxide (CO₂) additions via an in situ sparge system (CO₂ was used to neutralize the high pH produced from reactions in the iron wall). Groundwater was drawn through the gate by pumping two wells located at the sealed, downgradient, end. Over a 4-month period an estimated 1350 g of cDCE flowed into the treatment gate and the iron wall removed 1230 g, or 91% of the mass. The influent mass of VC was 572 g and the iron wall removed 535 g, corresponding to 94% mass removal. The other chlorinated ethenes had significantly lower influent masses (3 to 108 g) and the iron wall removed the majority of the mass resulting in >96% mass removal for any of the compounds. In spite of these high removal percentages, laboratory column tests indicated that at these levels of chlorinated contaminants, surface saturation of the iron grains likely contributed to lower than expected reaction rates. In the biosparge zone, mass removal of cDCE appeared to occur predominantly by biodegradation (65%) with volatilization (35%) being an important secondary process. The dominant removal process for VC was volatilization (70%) although significant biodegradation was also indicated (30%). Laboratory microcosm results confirmed the potential for aerobic biodegradation of cDCE and VC. When average influent field concentrations for cDCE and VC were 220,000 and 46,000 μg/l, respectively, the sequential treatment unit removed 99.6% of the total mass and when the influent concentrations decreased to 26,000 and 19,000 μg/l for cDCE and VC, respectively, >99.9% removal within the treatment gate was attained. BTEX compounds were found to be significantly retarded in the iron treatment zone. Although they did eventually break through the granular iron, and into the gravel transition zone, none of these compounds was detected in the biosparge zone. No noticeable interferences between the anaerobic (reductive) and aerobic parts of the system occurred during testing. The results of this experiment show that in situ treatment sequences are viable, although further work is needed to optimize performance.     

Plant-promoted pyrene degradation in soil

A study was conducted to investigate the capability of nine plant species to promote the degradation of pyrene in soil. The test method allowed for analysis of the entire sample of soil. More pyrene was degraded in the presence of roots of all nine species than in unplanted soil. Within approximately 8 weeks, as much as 74% of the pyrene disappeared from vegetated soil compared to 40% or less from unplanted soil. The data suggest that some of the test species may be especially useful for phytoremediation of soils contaminated with PAHs.