Lars Öberg

Sources, Fate, and Toxic Hazards of Oxygenated Polycyclic Aromatic Hydrocarbons (PAHs) at PAH- contaminated Sites

Abstract In this paper we show that oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) are important cocontaminants that should be taken into account during risk assessment and remediation of sites with high levels of PAHs. The presented data, which have been collected both from our own research and the published literature, demonstrate that oxy-PAHs are abundant but neglected contaminants at these sites. The oxy-PAHs show relatively high persistency and because they are formed through transformation of PAHs, their concentrations in the environment may even increase as the sites are remediated by methods that promote PAH degradation. Furthermore, we show that oxy-PAHs are toxic to both humans and the environment, although the toxicity seems to be manifested through other effects than those known to be important for polycyclic aromatic compounds in general, that is, mutagenicity and carcinogenicity. Finally, we present data that support the hypothesis that oxy-PAHs are more mobile in the environment than PAHs, due to their polarity, and thus have a higher tendency to spread from contaminated sites via surface water and groundwater. We believe that oxy-PAHs should be included in monitoring programs at PAH-contaminated sites, even if a number of other toxicologically relevant compounds that may also be present, such as nitro-PAHs and azaarenes, are not monitored. This is because oxy-PAH levels are difficult to predict from the PAH levels, because their environmental behavior differs substantially from that of PAHs, and oxy-PAHs may be formed as PAHs are degraded.

Pressurised liquid extraction of polycyclic aromatic hydrocarbons from contaminated soils

The reliability and efficiency of the pressurised liquid extraction technique (PLE) for extracting polycyclic aromatic hydrocarbons (PAHs) from contaminated soil has been investigated. Experimental design was used to study the influence of seven extraction variables (sample load, solvents used, solvent ratios, pressure, temperature, extraction time, and rinse volume). The results show that large sample loads in combination with small solvent volumes may result in low extraction efficiency. They also indicate that the recovery of low-molecular-mass PAHs is reduced by low extraction temperatures. The exact settings of the other variables are, however, less significant for the extraction efficiency. Repeated extractions at optimised settings of the tested variables show that PLE is an exhaustive extraction technique that generally results in high yields. In addition, extraction of a certified reference material (CRM 103-100) revealed that the method is both accurate and precise. Another finding was that adding the internal standard on top of the soil in the extraction cell causes considerable over-estimation of the concentrations when large samples are extracted with small solvent volumes. This is because the PLE-cell resembles a chromatographic column, so compounds added to the top of the soil layer have a longer distance to travel through the soil compared to the average distance of the native compounds, which are distributed evenly throughout the column. We therefore recommend that the internal standard should be added to the extract immediately after the extraction or, alternatively, carefully mixed with the sample prior to extraction.

Early complications after anterior dislocation of the shoulder in patients over 40 years : an ultrasonographic and electromyographic study

The rate of complications after anterior dislocation of the shoulder was evaluated in 65 patients aged over 40 years. 36 of 55 cases had electromyographically verified axillary nerve or brachial plexus injury. Rotator-cuff lesion was seen in 24 of the 63 sonographically examined cases. At follow-up in a telephone interview on average 3 years after the injury, 27 of the 57 cases had complaints from their shoulder. The incidence of initial nerve and/or cuff lesions was higher in those with persisting symptoms at follow-up.

Biochemical formation of PCDD/Fs from chlorophenols

Abstract Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) can be formed via biochemical transformation of chlorophenols (CPs). Experiments in vitro have shown that peroxidases in the presence of hydrogen peroxide can catalyze this reaction. So far, we have tested eight CPs, including pentachlorophenol (PeCP). All CPs gave PCDD/Fs. PeCP formed 0.1 mg OCDD per g PeCP. The reaction, the yield and the product mixture of PCDD/Fs are dependent upon which CP isomer is oxidized.

Peroxidase-catalyzed oxidation of chlorophenols to polychlorinated dibenzo-p-dioxins and dibenzofurans

Chlorophenols are transformedin vitro to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/ Fs) by peroxidase-catalyzed oxidations. This is demonstrated with bovine lactoperoxidase as well as horseradish peroxidase, and with 3,4,5- and 2,4,5-trichlorophenol (TrCP). The yield of total PCDD/Fs with lactoperoxidase was 11 μg per g 345-TrCP and 10 μg per g 245-TrCP, of which 2,3,7,8-substituted PCDD/Fs constituted 8.5 and 2.2 μg/g, respectively, corresponding to 0.85 and 1.2 μg/g of Nordic TCDD-equivalents.

Use of a column leaching test to study the mobility of chlorinated HOCs from a contaminated soil and the distribution of compounds between soluble and colloid phases

An equilibrium and recirculation column test for hydrophobic organic chemicals (ER-H test) was used to study the leaching behaviour of chlorophenols (CPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) from contaminated soil. A 50% increase in the pore water velocity was shown to have little or no effect on the mobility of CPs, PCDEs, PCDFs and PCDDs. The standard deviations of truly dissolved compounds, CPs, were between 19% and 65% between the tests. However, the repeatability of the ER-H test decreased with increases in the hydrophobicity of the studied compounds; the standard deviations for PCDEs, PCDFs and PCDDs ranged from 53% to 110%, 57% to 77% and 110% to 130%, respectively. The influence of colloids on the release of these compounds was also examined. Up to 30% of the CPs in the soil were leached, of which 1-3% were associated with colloids. The PCDEs, PCDFs and PCDDs were found to be preferably associated with the particulate fraction of the leachate, and less than 0.2% of these compounds were mobilised.

The transformation of chlorophenols by lactoperoxidase

The lactoperoxidase-catalyzed transformations of penta-,2,3,4,6-tetra-, 2,4,6-tri-, 2,4-di- and 4-monochlorophenol were followed spectrophotometrically. Apparent stoichiometries of chlorophenol:H2O2 ranged from 1:1 for the tri- and tetrachlorophenol at pH7 to 5:2 for pentachlorophenol at pH 4. The initial velocity (v0) was only slightly influenced by changes in [H2O2] greater then 5 microns. v0 responded to [chlorophenol] according to the empirical expression v0=[lactoperoxidase] . (k1[chlorophenol] + k2[chlorophenol]2). The constant k1 was trichlorophenol, respectively, at pH 7. With the di- and monochlorophenol the solution soon became opaque, and the reaction ceased. The results show that more than one reaction occurs. Some comparisons were also made with horseradish peroxidase A and C. Cetyltrimethylammonium bromide prevented opaqueness, but was shown to be a substrate for lactoperoxidase. Assuming an average concentration of 0.1 microns for H2O2 and pentachlorophenol in man, the metabolic rate becomes 30 ng/h per g of peroxidase-containing tissue, possibly with deposition of the products.

Mutagenicity of an aged gasworks soil during bioslurry treatment

This study investigated changes in the mutagenic activity of organic fractions from soil contaminated with polycyclic aromatic hydrocarbons (PAHs) during pilot‐scale bioslurry remediation. Slurry samples were previously analyzed for changes in PAH and polycyclic aromatic compound content, and this study examined the correspondence between the chemical and toxicological metrics. Nonpolar neutral and semipolar aromatic fractions of samples obtained on days 0, 3, 7, 24, and 29 of treatment were assayed for mutagenicity using the Salmonella mutation assay. Most samples elicited a significant positive response on Salmonella strains TA98, YG1041, and YG1042 with and without S9 metabolic activation; however, TA100 failed to detect mutagenicity in any sample. Changes in the mutagenic activity of the fractions across treatment time and metabolic activation conditions suggests a pattern of formation and transformation of mutagenic compounds that may include a wide range of PAH derivatives such as aromatic amines, oxygenated PAHs, and S‐heterocyclic compounds. The prior chemical analyses documented the formation of oxygenated PAHs during the treatment (e.g., 4‐oxapyrene‐5‐one), and the mutagenicity analyses showed high corresponding activity in the semipolar fraction with and without metabolic activation. However, it could not be verified that these specific compounds were the underlying cause of the observed changes in mutagenic activity. The results highlight the need for concurrent chemical and toxicological profiling of contaminated sites undergoing remediation to ensure elimination of priority contaminants as well as a reduction in toxicological hazard. Moreover, the results imply that remediation efficacy and utility be evaluated using both chemical and toxicological metrics. Environ. Mol. Mutagen. 2009.

Stabilisation and development of the hip after closed reduction of late CDH

We used ultrasound to investigate the anatomy and stability of the hip during the phase of joint stabilisation after closed reduction of unilateral late CDH in 15 infants aged from two to 15 months. Conservative treatment by splintage in abduction led to complete stability in all hips in from three to 13 weeks. Immediately after reduction, interposed soft tissue caused lateralisation of the femoral head, but this progressively disappeared, and the initially smaller femoral head on the dislocated side regained normal size. Ultrasonic evaluation of the hip in late CDH is a valuable and safe tool; it reduces the need for radiographic examination and improves treatment by visualising the actual pathology. The more frequent use of ultrasound can reduce the need for open reduction in the age group that we studied.

On the absence of polychlorinated dibenzodioxins and dibenzofurans after lactoperoxidase-catalyzed transformation of chlorophenols.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) have been detected in many species and environments their bioresistance and toxicity being of great concern. PCDDs and PCDFs, or the predioxins and -furans, are formed from chlorophenols (CPs) by burning and pyrolysis by arcing and by photolysis. PCDDs and PCDFs have also been found in emissions from automobiles, municipal waste incinerators, and nickel and copper smelting. Peroxidases (POs), a group of heme-proteins, are found in many organs and organisms. They are exceptional enzymes because of low substrate specificity and multiple reaction mechanisms. This enzyme-catalyzed free radical reaction resembles reactions in pyrolysis, arcing, and photolysis. Halogenated phenols are among the peroxidase substrates, and phenolic substrates have been found to yield dibenzodioxin- and dibenzofuran like products. The question then arose whether CPs in peroxidase-mediated reactions could yield chlorinated dibenzodioxins and dibenzofurans. Since no-one has yet reported a biological formation of PCDDs and PCDFs the authors have analyzed the rpdoct mixture from the lactoperoxidase-catalyzed oxidation of some chlorophenols.