Photodegradation of pentachlorophenol and its degradation pathways predicted using density functional theory

The objectives of the present research were (i) to report the mass balance of chlorine during pentachlorophenol (PCP) photodegradation and (ii) to reveal the photodegradation pathway experimentally with a theoretical proof based on the density functional theory (DFT). The chlorine of PCP was completely mineralized to produce chloride ions after 24h of UV irradiation. As intermediates, 2,3,5,6-tetrachlorophenol, 2,3,4,6-tetrachlorophenol and 2,5-dichlorophenol were identified. At least 80% of the chlorine balance during PCP photodegradation was accounted by PCP, these intermediates, and chloride ions. A DFT calculation showed differences in the C-Cl bond dissociation energy level and the positions of respective PCP molecular and the PCP intermediates. The dechlorination intermediates predicted using the calculated C-Cl bond dissociation energy were consistent with those experimentally confirmed, indicating the feasibility of this theoretical method in predicting the dechlorination pathway.     

Local stakeholders' acceptance of model-generated data used as a communication tool in water management: The Rönneå Study

The objective of this study was to increase the knowledge of local stakeholders' acceptance of model-generated data when used as a communication tool in water quality management. The R?nne? catchment in the southwest of Sweden was chosen as the study area. The results indicate the model-generated data served as a uniting factor. Simultaneously, the stakeholders were concerned with presented data, the main problems being sources of pollution, which were not accounted for, lack of trustworthiness when measuring pollution, and the uncertainty of the impact of natural variation and delayed effects. Four clusters of factors were identified as influencing stakeholders' acceptance of the model-generated data: confidence in its practical applications, confidence in the people involved in or providing material for the dialog (such as experts, decision-makers, and media), the social characteristics of the participants (such as age and profession), and the way of communicating the data (such as tone of communication, group composition, duration, and geographical scope of the dialog). The perception of the fairness of the practical application of given model-generated data was also an important factor for acceptance.     

Estimating catchment nutrient flow with the HBV-NP model: sensitivity to input data

The dynamic catchment model HBV-N has been further developed by adding routines for phosphorus transport and is now called the HBV-NP model. The model was shown to satisfactorily simulate nutrient dynamics in the R?nne? catchment (1,900 km2). Its sensitivity to input data was tested, and results demonstrated the increased sensitivity to the selection of input data on a subcatchment scale when compared with the catchment scale. Selection of soil and land use databases was found to be critical in some subcatchments but did not have a significant impact on a catchment scale. Although acceptable on a catchment scale, using templates and generalization, with regards to emissions from point sources and rural households, significantly decreased model performance in certain subcatchments when compared with using more detailed local information. A division into 64 subcatchments resulted in similar model performance at the catchment outlet when compared with a lumped approach. Adjusting the imported matrixes of the regional leaching of nitrogen, from agricultural land, against mean subcatchment water percolation did not have a significant impact on the model performance.     

Growth of Plants on TBT-contaminated Harbour Sludge and Effect on TBT Removal (10 pp)

Background Worldwide, large amounts of sediments have to be dredged annually from waterways and harbours. These sediments are sometimes polluted with a variety of toxic compounds. In some countries, including Belgium, the load with the biocide tributyltin (TBT) from ship coatings prohibits the dumping of harbour sludge into the sea. Land-based dumping is a commonly used alternative. Objective This research investigated the feasibility to use land-deposited harbour sludge for plant production. In a field trial, the growth of 38 more or less salt-tolerant plant species on low and high TBT-contaminated sediments was studied. The elimination of TBT from sludge with and without vegetation was compared. The uptake of TBT and its degradation products di- and monobutyltin (DBT and MBT) into harvest products under field conditions was determined. - Experimental Set-up. Sediments dredged in May 2003 from the brackish waters of the port of Antwerp were analysed in the laboratory for soil texture, pH, electroconductivity, sodium, magnesium, potassium, calcium, ammonium, nitrate, total nitrogen, chloride, sulphur and the organotins TBT, DBT and MBT. The sediments were lagooned for one year to dewater, desalinate and improve their structure. Salt-tolerant domestic and wild plants were selected and sown in May 2004. In August 2004, plants were harvested and the produced biomass was determined. Samples were taken from vegetated and non-vegetated top and bottom sediments and from plants growing above soil and analysed for TBT, DBT and MBT. Results The fresh sediments showed a good supply with nutrients and a neutral pH, but were rather saline (EC 14 mS cm-1 of the saturated paste extract). The salinity decreased to 3.7 mS cm-1 during lagoonation. The high and the low contaminated sediment had initially 43 and 1.6 mg TBT kg-1 dry weight, respectively. Besides TBT, several other contaminants were present in the sediments at critical levels. The biomass production of the plant species from the field trial ranged from 0.2 to 13 tons dry mass per hectare. Plants performing excellently were barley, sorghum, rape seed, a clover/grass mix and reed. If at all, a positive influence of TBT on plant growth was seen. TBT was degraded significantly faster (>40%) below barley. The uptake of TBT, DBT and MBT into stem and leaves of reed, grass and clover was very low, but measurable and not related to concentrations in soil. No uptake of TBT or its metabolites into corn of barley was found. Discussion This study confirmed former results: the toxicity of TBT to higher plants is low, and even high levels in soils would not be a hindrance for crop production. The removal of TBT seemed to be increased by both lagooning and plant growth, although the target values for sea dumping in use in certain European countries were not reached. A plausible explanation for the faster degradation of TBT under vegetation is that oxygen is a limiting factor, and plants dewater the soil, thus aerating it. The uptake of the organotins TBT, DBT and MBT into harvest products is probably due to attached soil particles. Conclusions To summarize, barley was the optimal species: it grew very well despite the salinity of the dredged sediments, it had a significantly positive effect on TBT removal; it showed no measurable uptake of TBT or the other butyltins into the harvested product; and it is a cash crop well established in European agriculture. Outlook The amounts of dredged sediments are high, and good soils are becoming increasingly rare. The feasibility of using dredged sediments for non-food production, such as energy crops, should be investigated by a critical risk assessment.     

Temporal trends of organochlorine contamination in Black Guillemots in Iceland from 1976 to 1996

The levels of several different persistent organochlorines (OCs) in Black Guillemots Cepphus grylle, collected during the summers of 1976-1996 at Breioafj?rour in W-Iceland, were investigated. The levels of about 40 different organochlorines (PCBs, DDTs, chlordanes, toxaphenes, HCH, HCB) were compared with respect to age, sex, fat content, and year of collection. The levels of PCBs correlated very closely with those of DDE, indicating long-range transport as the major source of these contaminants in Iceland, with the ratio PCBs/DDE mostly in the range of 2-5. Unlike the Gyrfalcon Falco rusticolus, the organochlorine levels did not seem to accumulate substantially with age, neither in males nor females. The variation in the levels of OCs at the age of 2 years was even greater than the variation in OC levels over an age range of 12 years. In immature birds the levels of PCBs, DDE, HCB and beta-HCH declined very slowly (T(1/2) from 12 to 20 years) over the years 1976-1996, whereas the levels of alpha-HCH and p,p'-DDT declined much faster. The levels of trans-nonachlor, alpha-chlordane, gamma-chlordane, oxychlordane, and toxaphene did not correlate with the year of collection. As the Black Guillemot is mostly a resident seabird, feeding mainly on small fish and invertebrates, this investigation should give a good indication of the temporal trends of organochlorine pollution at Breioafj?rour, Iceland, during this 20 year period and is likely to reflect baseline trends in the marine environment of the North-Atlantic Ocean.     

Laboratory simulation of biodegradation of chemicals in surface waters: closed bottle and respirometric test

Microbial degradation is the most dominant elimination mechanism of organics from the environment. For evaluation of biodegradability of pure chemicals many standardized tests are available, but no standardized procedure for assessment of biodegradability of chemicals in surface water is agreed upon. Rates of in-situ biodegradation are usually estimated in laboratory simulation where environmental factors are reproduced to some extent. The aim of our study was to compare standardised ready biodegradability assessment, test (Closed bottle test) and its modifications employing the basic agreements on test conditions to simulate biodegradation in surface water. Standard test was modified using various natural river waters to simulate the natural environment in a simplified way. The impact of different types and amounts of nutrients and microorganisms on biodegradation was confirmed. The conditions in the recipient should be examined to extrapolate the results from ready biodegradability tests to real surface water.     

Tissue distribution of planar and non-planar chlorobiphenyls, 4,4'-DDE and hexachlorobenzene in sheep and lambs

The bioconcentration and distribution pattern of individual PCB congeners (IUPAC Nos: -54, -80, -155 and -169) and organochlorine pesticides (HCB and 4,4'-DDE) in blood, adipose tissue, liver and brain were examined in sheep two months after administration and in their offspring continuously exposed during the two months lactation period. Analyses were performed by high resolution gas chromatography. The levels of individual organochlorines varied significantly between tissues; the tissue/blood ratio (on a fat basis) varied by two orders of magnitude for individual congeners. The bioconcentration of the toxic planar PCB-169 congener was the highest in the liver and the lowest in the brain of the sheep.     

Interactive effects of ozone and elevated carbon dioxide on the growth and physiology of black cherry, green ash, and yellow-poplar seedlings

Potted seedlings of black cherry (Prunus serotina Ehrh.) (BC), green ash (Fraxinus pennsylvanica Marsh.) (GA), and yellow-poplar (Liriodendron tulipifera L.) (YP) were exposed to one of the four treatments: (1) charcoal-filtered air (CF) at ambient CO(2) (control); (2) twice ambient O(3) (2 x O(3)); (3) twice ambient CO(2) (650 microl l(-1)) plus CF air (2 x CO(2)); or (4) twice ambient CO(2) (650 microl l(-1)) plus twice ambient O(3) (2 x CO(2) + 2 x O(3)). The treatments were duplicated in eight continuously stirred tank reactors for 10 weeks. Gas exchange was measured during the last 3 weeks of treatment and all seedlings were destructively harvested after 10 weeks. Significant interactive effects of O(3) and CO(2) on the gas exchange of all three species were limited. The effects of elevated CO(2) and O(3), singly and combined, on light-saturated net photosynthesis (A(max)) and stomatal conductance (g(s)) were inconsistent across species. In all three species, elevated O(3) had no effect on g(s). Elevated CO(2) significantly increased A(max) in GA and YP foliage, and decreased g(s) in YP foliage. Maximum carbon exchange rates and quantum efficiencies derived from light-response curves increased, while compensation irradiance and dark respiration decreased in all three species when exposed to 2 x CO(2). Elevated O(3) affected few of these parameters but any change that was observed was opposite to that from exposure to 2 x CO(2)-air. Interactive effects of CO(2) and O(3) on light-response parameters were limited. Carboxylation efficiencies, derived from CO(2)-response curves (A/C(i) curves) decreased only in YP foliage exposed to 2 x CO(2)-air. In general, growth was significantly stimulated by 2 x CO(2) in all three species; though there were few significant growth responses following exposure to 2 x O(3) or the combination of 2 x CO(2) plus 2 x O(3). Results indicate that responses to interacting stressors such as O(3) and CO(2) are species specific.     

Polycyclic aromatic compounds in Northwest Atlantic COD (Gadus morhua)

Twenty-seven polycyclic aromatic compounds (PAC) including polycyclic aromatic hydrocarbons (PAH) and polycyclic aromatic sulphur heterocycles were analysed in muscle, liver and ovaries of cod (Gadus morhua) from the Northwest Atlantic. These PAC include the 16 PAH priority pollutants (EPA recommendation), alkylated naphthalenes, phenanthrene-anthracenes as well as dibenzothiophenes (DBT). Aromatics were undetectable in muscle. One of the analysed PAC was detected in one ovary and six in another ovary sample. Liver samples contained between 1 and 9 PAC. Of the parental PAH, only acenapthene (18 ng/g, dry weight), fluorene (28 ng/g) and chrysene (22 ng/g) were detected once each in two liver samples, while fluorene (72 ng/g) was detected once in one of the ovaries. C-2 DBT was the major component in ovaries and liver (8-86 ng/g), while C-3 and C-4 alkylated phenanthrene-anthracene (12-78 ng/g) were the next major components detected in the liver samples. This is the first detailed study of PAH and PAC in finfish from the Northwest Atlantic.