Development of a simple selective SFE method for the determination of desorption behaviour of PCBs in two Swedish sediments

A simple selective supercritical fluid extraction (SFE) method was developed for the determination of desorption behaviour of PCBs in sediments. This method was applied to determine the distribution of individual PCB congeners among sites of differing bonding strengths in two Swedish sediments (Lake J?rnsj?n and Baltic bay Orserumsviken). Four different PCB fractions were distinguished in each sediment by applying consecutively harsher supercritical fluid extraction conditions on the same sample. Even though the two sediments had completely different textures, they showed very similar extraction behaviour. It was shown that, in both sediments, a major part of the PCBs (58% and 65%, respectively) were located at "fast sites", from which they were extractable already with the mildest extraction conditions (60 min, 40 degrees C and 120 bar). Only a small fraction of the PCBs were so tightly bound to the sediments (located at "slow sites"), that they could be extracted only under the harshest conditions (60 min, 150 degrees C and 400 bar). Information of this kind should be of great value for the determination of bioavailability of pollutants in sediments and soils, and it is the author's belief that this technique has the potential to develop into a powerful tool in environmental risk assessment.     

Time series study of concentrations of SO4(2-) and H+ in precipitation and soil waters in Norway

Along with a steady reduction of acid inputs during 14 years of intensive forest monitoring in Norway, the influence of acid deposition upon soil water acidity is gradually reduced in favour of other and internal sources of H+ and sulphate, in particular from processes in the upper soil layer. We used statistical analyses in two steps for precipitation, throughfall and soil water at 5, 15 and 40 cm depths. Firstly, we employed time series analyses to model the temporal variation as a long-term linear trend and a monthly variation, and by this filtered out residual, weekly variation. Secondly, we used the parameter estimates and the residuals from this to show that the long term, the monthly and the weekly variation in one layer were correlated to similar temporal variation in the above, adjacent layer. This was strongly evident for throughfall correlated to precipitation, but much weaker for soil water. Continued acidification in soil water on many plots suggests that the combined effects of anthropogenic and natural acid inputs exceed in places the buffering capacity of the soil.     

Acute toxicity of chlorophenols to earthworms using a simple paper contact method and comparison with toxicities to fresh water organisms

An acute toxicity test of chlorophenols on earthworms (Eisenia fetida) was performed using a simple paper contact method proposed by OECD testing guideline no. 207, that were applied as an earthworm toxicity test. The median lethal concentration, EC50, had significant correlation with logP(ow) (1-octanol/water partition coefficient) of the chemicals. The toxicity of chlorophenols on E. fetida was compared with toxicities for other species: an algae (Selenostrum capricornutum), a crustacean (Daphnia magna), and a fish (Oryzias latipes). It was found that the toxicity of chlorophenols was almost same for E. fetida and for fresh water organisms. These results suggest the possibility of drawing correlations between the effects of pollutants on living things in different environments, fresh water and soil.     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

Evaluation of the stability of arsenic immobilized by microbial sulfate reduction using TCLP extractions and long-term leaching techniques

An investigation was conducted to evaluate the stability or leachability of arsenic immobilized by microbial sulfate reduction. Anoxic solid-phase samples taken from a bioreactor previously used to treat metal and As contaminated water using sulfate reducing bacteria (SRB) were subjected to the toxicity characteristic leaching procedure (TCLP) and long-term column leaching tests. The results from TCLP experiments showed that the concentration of As leached from solid-phase sulfide material (SSM) samples after an 18 h extraction time was <300 microgl(-1), which is below the current maximum Australian TCLP leachate value for As, and thus would not be characterized as a hazardous waste. In terms of percent total As leached, this was equivalent to <8.5% for SSM samples initially containing 61.3 mgkg(-1) As. The levels of As extracted by the TCLP was found to be significantly lowered or underestimated in the presence of dissolved oxygen, with As concentrations increasing with decreasing headspace-to-leachant volume ratios. The concentration of As was also consistently higher in nitrogen purged extractions compared to those performed in air. This was attributed to the dissolution of Fe-sulfide precipitates and subsequent oxidation of Fe(II) ions and precipitation of ferric(hydr)oxides, resulting in the adsorption of soluble As and corresponding decrease in As concentrations. According to the experimental data, it is recommended that TCLP tests for As leachability should be performed at least in zero-headspace vessels or preferably under nitrogen to minimize the oxidation of Fe(II) to ferric(hydr)oxides. In long-term leaching studies (approximately 68 days), it was found that the low solubility of the SSM ensured that rate of release of As was relatively slow, and the resulting leachate concentrations of As were below the current Australian guideline concentration for arsenic in drinking water.     

Near-field dispersion modeling for regulatory applications

This paper evaluates the application of dispersion models to estimate near-field pollutant concentrations in two case studies. The Industrial Source Complex Short-Term Model (ISCST3) was evaluated with hexavalent chromium measurements collected within 100 m of two facilities in Barrio Logan, San Diego, CA. ISCST3 provided reasonable estimates for higher pollutant concentrations but underestimated lower concentrations. To understand the observed distribution of concentrations in Barrio Logan, a recently conducted tracer experiment was analyzed. The tracer, sulfur hexafluoride, was released at ambient temperature from an urban facility at the University of California at Riverside, and concentrations were measured within 20 m of the source. Modeling results indicated that Industrial Source Complex-Plume Rise Model Enhancement and American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model-Plume Rise Model Enhancement overestimated high concentrations and underestimated low concentrations. A diagnostic study with a simple Gaussian dispersion model that incorporated site-specific meteorology was used to evaluate model results. This study found that incorporating lateral meandering for nonbuoyant urban plumes in Gaussian dispersion models could improve concentration estimates even when downwash is not considered. Incorporating a meandering component in ISCST3 resulted in improvements in estimating hexavalent chromium concentrations in Barrio Logan. Credible near-source concentration estimates depend on accurate characterization of emissions, onsite micrometeorology, and a method to account for lateral meandering in the near field.     

PCDDs/PCDFs and coplanar PCBs in eels (Anguilla anguilla) from different areas of the rivers Havel and Oder in the state of Brandenburg (Germany)

In 1996 forty-nine eels were caught from different locations along the rivers Oder (Hohenwutzen and Schwedt) and from 11 locations along the Havel river. They were analysed for PCDDs/PCDFs and the coplanar PCBs (PCB 77, PCB 126, PCB 169). Their contribution to 2,3,7,8-TCDD equivalents were estimated. In case of PCDDs/PCDFs these amounted between 1.8 and 15.2 pg/g fat (mean 6.1 pg/g; median 5.2 pg/g), in case of coplanar PCBs between 2.4 and 170.5 pg/g fat (mean 47.7 pg/g; median 36.1 pg/g). Lakes which are associated with but not directly located at the main stream of the river Havel contributed much less to contamination of the eels than the river segments situated in the more urbanised or industrialised sites along the main river.     

Use of lees materials as an adsorbent for removal of organochlorine compounds or benzene from wastewater

Lees materials such as wheat bran, rapeseed, linseed, okara (lees of bean curd), and sakekasu (sake lees) were found to effectively adsorb organochlorine compounds. The amounts of these compounds such as chloroform, dichloromethane, and benzene adsorbed were plotted against the equilibrium concentration of substances in solution on a logarithmic scale. A linear relationship was obtained, indicating that the adsorption reactions were of the Freundlich type. When the lees materials were applied to wastewater (pH: 10) containing 0.1 g/l of dichloromethane, dichloromethane was removed from the wastewater in the range of 70-90% efficiency after 90 min. There was a high correlation between the removal efficiency and the number of spherosomes, which are intracellular particles attributed to the uptake of organochlorine compounds.     

Occurrence of organotin compounds in house dust in Berlin (Germany)

In a study in the year 2000 on the occurrence of hazardous environmental contaminants house dust samples from 28 Berlin apartments were measured for the presence and concentrations of six organotin compounds, monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monooctyltin (MOT), dioctyltin (DOT) and triphenyltin (TPT). The concentrations of MBT and DBT determined ranged considerably from 0.01 mg kg-1 to 1.5 mg kg-1 (median: 0.05 mg kg-1) and 0.01 to 5.6 mg kg-1 (median: 0.03 mg kg-1), respectively. Maximum levels of TBT and MOT were only 0.08 mg kg-1 and 0.04 mg kg-1. The maximum total value of the organotins was 7.2 mg kg-1 (median: 0.11 mg kg-1). MBT was found in 86% and DBT in 82% of the samples above the limit of quantification, TBT and MOT only in 50% and DOT in 43%. The focus of ecotoxicology is on the risks arising from organotin compounds (especially butyltins) when used as biocides in antifouling paints. TBT acts as an endocrine disrupter in animals, inducing masculinization (imposex) in female gastropods of different species by increasing testosterone levels. The most critical organ site in experimental animals is the cellular immune system, where lymphocyte depletion in the thymus and peripheral lymphoid tissues takes place. Our study does not provide data on the basis of which population exposure could be estimated; house dust containing harmful organotins could, however, under some conditions, become a relevant intake possibility for young children.     

Degradation of the antifouling compound Irgarol 1051 by manganese peroxidase from the white rot fungus Phanerochaete chrysosporium

Irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine), a derivative of s-triazine herbicide, is an antifouling compound used as an alternative to organotins. The compound is highly persistent and is known to be biodegraded only by the white rot fungus, Phanerochaete chrysosporium. We used partially purified manganese peroxidase (MnP) prepared from P. chrysosporium to evaluate its capacity to degrade Irgarol 1051. MnP degraded Irgarol 1051 to two major products, one identified as M1 (identical to GS26575, 2-methylthio-4-tert-butylamino-6-amino-s-triazine) and the other not identified but with same mass spectrum as M1 and a different ultraviolet spectrum. This report clearly demonstrates that this ligninolytic enzyme is involved in the degradation of Irgarol 1051.