Intra- and inter- laboratory variability in paper industry PCDD/PCDF analysis

Studies were conducted to quantify variability for pulp industry wastewater effluent, pulp and sludge analyses. Intralaboratory variability studies indicated that there is a potential for greater between batch variability in results than for within a batch. Intralaboratory relative standard deviations for replicate analyses ranged from 6% to 60%. Interlaboratory studies, using standard reference materials showed relative standard deviations from 4% to 135%. There appeared to be little dependance of variability on concentration, suggesting matrix effects were very important. In general, effluent variability was greater than observed for pulps or sludges. Analysis of reference standards indicated that 13% to 17% variability can be attributed to differences in calibration standards. A limited study of full congener PCDD/PCDF analysis variability showed it to be greater than observed for TCDD/TCDF.     

Sorption of linear alcohol ethoxylate surfactant homologs to soils

Sorption onto five saturated soils of the homologs within the commercial surfactant mixture Brij 35 (registered trademark of ICI Americas) was investigated. Brij 35 is a mixture of linear ethoxylated alcohols, having an average of 23 ethoxy (EO) groups per molecule and alcohol chain of primarily 12 carbons in length (C₁₂H₂₅(OCH₂CH₂)₂₃OH). In experiments, saturated soils were exposed to various concentrations of the surfactant mixture for specified times, the slurries were centrifuged to separate the phases, the aqueous phases were extracted with 1,2-dichloroethane, and the residual homologs were derivatized with 3,5-dinitrobenzoyl chloride and analyzed by normal phase HPLC. Homologs containing 4–43 EO groups were chromatographically separated at near baseline. At aqueous Brij 35 concentrations below the critical micelle concentration (cmc), the proportion of each homolog sorbed to each of the soils increased with increasing EO chain length through the homologous series. As a result, in experiments where a significant proportion of the surfactant adsorbed, significant shifts in the aqueous phase compositions occurred to mixtures with lower mean EO numbers. A sharp break in the adsorption isotherms occurs at the cmc.     

Migration behavior of naturally occurring radionuclides at the Nopal I uranium deposit, Chihuahua, Mexico

Oxidation of pyrite at the Nopal I uranium deposit, Peña Blanca district, Chihuahua, Mexico has resulted in the formation of Fe-oxides/hydroxides. Anomalous U concentrations (i.e. several hundred to several thousand ppm) measured in goethite, hematite, and amorphous Fe-oxyhydroxides in a major fracture that crosscuts the deposit and the absence of U minerals in the fracture suggest that U was retained during secondary mineral growth or sorbed on mineral surfaces. Mobilization and transport of U away from the deposit is suggested by decreasing U concentrations in fracture-infilling materials and in goethite and hematite with distance from the deposit. Greater than unity ²³⁴U/²³⁸U activity ratios measured in fracture-infilling materials indicate relatively recent ( < 1 Ma) U uptake from fluids that carried excess ²³⁴U. Systematic decreases in ²³⁴U/²³⁸U activity ratios of fracture materials with distance from the deposit suggest a multistage mobilization process, such as remobilization of U from ²³⁴U-enriched infill minerals or differential or diminished transport of U-bearing solutions containing excess ²³⁴U.     

The SeKT joint research project: definition of reference conditions, control sediments and toxicity thresholds for limnic sediment contact tests

- In current biotest approaches, intact organisms or in vitro systems are exposed to sediments using different exposure scenarios. The most important issue in sediment toxicity testing protocols is the question which test phase (solid or liquid) should be used. Whole-sediment exposure protocols represent the most realistic scenario to simulate in situ exposure conditions in the laboratory. However, until now there is no agreement in how to acquire and to evaluate the data of the various available sediment contact assays. The SeKT joint research project was initiated with the aim to compare recently developed sediment contact assays by addressing reference conditions, control sediments and toxicity thresholds for limnic sediment contact tests.     

Investigation of unrecognized former secondary lead smelting sites: confirmation by historical sources and elemental ratios in soil

Twelve suspected former secondary lead smelting sites were investigated. Ten of the sites were confirmed to be former secondary lead smelters or lead works by historical fire insurance maps and contemporaneous metal industry trade directories. At eight sites sampled, the ratio Sb:Pb was closer to ratios from 10 known lead smelting sites than were the As:Pb and Cd:Pb ratios. Data from the 10 known lead smelting sites showed that the Sb:Pb ratio is most characteristic of secondary lead smelting sites. This is because the primary alloy smelted at such sites is antimonial lead. Lead contamination at the eight sites investigated here can be attributed At least in part to the former smelters because of the association between Sb and Pb.     

Inhibition of retinoid activity by components of a paper mill effluent

Few studies have evaluated PCB concentrations in alligators. This is the first comparison of PCB concentrations in alligators eggs from the southeastern United States. Eggs were collected from Bear Island and Winyah Bay, South Carolina and from the Rockefeller Wildlife Refuge, Louisiana. Mean PCB concentrations in eggs from Bear Island (333 ng/g) were the same (P > 0.45) as those found at the Rockefeller Wildlife Refuge (218 ng/g). However, eggs from Winyah Bay contained 3176 ng/g PCBs which is higher (P < 0.008) than concentrations from the other two sites. These data indicate the ubiquitous nature of PCBs and their bioaccumulation even in remote habitats.     

An analytical quantification of mass fluxes and natural attenuation rate constants at a former gasworks site

A new integral groundwater investigation approach was used for the first time to quantify natural attenuation rates at field scale. In this approach, pumping wells positioned along two control planes were operated at distances of 140 and 280 m downstream of a contaminant source zone at a former gasworks site polluted with BTEX- (benzene, toluene, ethyl-benzene, o-, p-xylene) and PAH- (polycyclic aromatic hydrocarbons) compounds. Based on the quantified changes in total contaminant mass fluxes between the control planes, first-order natural attenuation rate constants could be estimated. For BTEX-compounds, these ranged from 1.4e-02 to 1.3e-01 day(-1) whereas for PAH-compounds natural attenuation rate constants of 3.7e-04 to 3.1e-02 day(-1) were observed. Microbial degradation activity at the site was indicated by an increase in dissolved iron mass flux and a reduction in sulphate mass flux between the two investigated control planes. In addition to information about total contaminant mass fluxes and average concentrations, an analysis of the concentration-time series measured at the control planes also allowed to semi-quantitatively delineate the aquifer regions most likely contaminated by the BTEX- and PAH-compounds.     

Evaluation of the genotoxic and cytochrome P450 monooxygenase-inhibitory potential of Dicuran on procaryotic and eucaryotic test systems

The effect of the herbicide Dicuran 500 FL (formulated product) on the phenotypical and genotypical changes in procaryotic and eucaryotic organisms was investigated using short-term tests for detecting genotoxins. Since pesticides discharged in the water environment can modulate the mixed-function monooxygenases (MFO) detoxification system of water organisms, the in vivo and in vitro effects of Dicuran on hepatic cytochrome P450 (cyt P450) monooxygenase activities were also examined in juvenile carp (Cyprinus carpio L.). By measuring the activities of MFO in experimental carp exposed to Dicuran an attempt was made to establish whether Dicuran could be bioactivated by MFO into ultimate mutagens. Our results on the bacterial strains Salmonella typhimurium TA100 and TA98 show that Dicuran does not possess either mutagenic or premutagenic characteristics. The micronucleus test on the erythrocytes of experimental carp did not establish any clastogenic effect either. However, Dicuran significantly inhibited the MFO activity of 7-ethoxyresorufin-O-deethylase (EROD) and benzo[a]pyrene monooxygenase (BaPMO) in the liver of experimental carp in vitro, as well as in in vivo conditions. These findings demonstrate the potentially damaging effect of Dicuran on the xenobiotic metabolizing enzyme systems of fish, and suggest the applicability of described methods for the prediction of the ecotoxicological significance of the presence of pesticides in the water environment.     

An assessment of the risks associated with polychlorinated biphenyls found in the stomach contents of stranded Indo-Pacific Humpback Dolphins (Sousa chinensis) and Finless Porpoises (Neophocaena phocaenoides) from Hong Kong waters

The risks to Indo-Pacific Humpback Dolphins and Finless Porpoises associated with polychlorinated biphenyls (PCBs) were assessed. Stomach contents from twelve stranded Humpback Dolphins and sixteen stranded Finless Porpoises were collected. Concentrations of total and isomer-specific PCBs in the stomach contents were determined using dual-column gas chromatography equipped with electron capture detectors (GC-ECD). Risks due to the PCBs were assessed in three scenarios, based on total PCBs (summation of 41 PCB congeners), total toxicity equivalency (TEQs) and PCB 118, using the toxicity reference values (TRVs) as the threshold effects benchmarks. The calculated risk quotients (RQs) showed that risks due to PCBs were generally low or negligible. Specifically, RQs from total TEQs and total PCBs for Finless Porpoises are below one, suggesting that PCBs should be a low risk for the Finless Porpoise in Hong Kong waters. However, the Humpback Dolphin has RQs larger than 1 for total TEQs and total PCBs when the 95th percentile data were used in the evaluation. This indicates that further investigation may be needed to examine more closely the potential impact of toxic contaminants in the habitat of the Humpback Dolphin.