Determination of 99Tc deposited on the ground within the 30-km zone around the Chernobyl reactor and estimation of 99Tc released into atmosphere by the accident

Technetium-99 was determined in samples from the 30-km zone around the Chernobyl reactor. Concentrations of ⁹⁹Tc in soil samples taken from three forest sites ranged from 1.1 to 14.1 Bq kg⁻¹ dry weight for the organic soil layers, and from 0.13 to 0.83 Bq kg⁻¹ dry weight for the mineral soil layers. In particular, for the organic layers, the measured ⁹⁹Tc concentrations were one or two orders of magnitude higher than those due to global fallout ⁹⁹Tc. The ⁹⁹Tc depositions (Bq m⁻²), based on the sum of the depositions measured in organic and mineral layers, ranged from 130 Bq m⁻² within the 10-km zone to about 20 Bq m⁻² close to the border of the 30-km zone. Taking the corresponding measured ¹³⁷Cs depositions into account, it was found that the activity ratio of ⁹⁹TW/¹³⁷Cs ranged from 6 × 10⁻⁵ to 1.2 × 10⁻⁴. It was estimated that about 970 GBq of ⁹⁹Tc had been released by the Chernobyl accident. This figure corresponded to 2%–3% of the total ⁹⁹Tc inventory in the core.     

Results from the first year of the Swedish dioxin survey

PCDD/F levels are presented for food baskets, raw and fried herring, wolf muscle and moose tallow collected from the same area, three burbot liver samples, a sediment core from the Baltic Sea and leach water from three garbage dumps. Levels in food baskets were at or below detection limits making the estimation of intake via the diet difficult. Frying herring produces no net change in PCDD/F levels. Moose have lower PCDD/F levels than wolf from the same area. Levels in burbot liver samples are much higher near industrial discharges than in a more undisturbed area. The top 4 cm of the sediment core contain the highest levels of PCDD/F. Thereafter the levels drop and reach a low level. This low level is probably caused by contamination during sampling and is not evidence of PCDD/F presence far back in time. Leach water from city dumps contains low levels of PCDD/F but that from a dump that takes industrial wastes had higher levels and a different congener pattern.     

Experimental determination of the kinetic rate law for the oxidation of perchloroethylene by potassium permanganate

Flushing soils contaminated with trichloroethylene (TCE) and perchloroethylene (PCE) with a permanganate (MnO₄⁻) solution has been shown to reduce the solvent content of the soil. Experiments were performed to quantify the rate at which KMnO₄ oxidizes aqueous solutions of PCE over a range of concentrations. In a series of homogeneous reactors, aqueous phase PCE concentrations were monitored over time in nine experimental trials with excess oxidant concentrations ranging from 5 to 30 g/l. Analysis of the data was performed to quantify the oxidation reaction order with respect to PCE and KMnO₄ and the reaction rate constant. The reaction between PCE and KMnO₄ was determined to be first-order with respect to both PCE and KMnO₄ with an overall specific reaction rate coefficient of 2.45±0.65 M⁻¹ min⁻¹.     

β-Estradiol and ethinyl-estradiol contamination in the rivers of the Carpathian Basin

17β-Estradiol (E2) and 17α-ethinyl estradiol (EE2), which are environmental estrogens, have been determined with LC-MS in freshwater. Their sensitive analysis needs derivatization and therefore is very hard to achieve in multiresidue screening. We analyzed samples from all the large and some small rivers (River Danube, Drava, Mur, Sava, Tisza, and Zala) of the Carpathian Basin and from Lake Balaton. Freshwater was extracted on solid phase and derivatized using dansyl chloride. Separation was performed on a Kinetex XB-C18 column. Detection was achieved with a benchtop orbitrap mass spectrometer using targeted MS analysis for quantification. Limits of quantification were 0.05 ng/L (MS1) and 0.1 ng/L (MS/MS) for E2, and 0.001 ng/L (MS1) and 0.2 ng/L (MS/MS) for EE2. River samples contained n.d.–5.2 ng/L E2 and n.d.–0.68 ng/L EE2. Average levels of E2 and EE2 were 0.61 and 0.084 ng/L, respectively, in rivers, water courses, and Lake Balaton together, but not counting city canal water. EE2 was less abundant, but it was still present in almost all of the samples. In beach water samples from Lake Balaton, we measured 0.076–0.233 E2 and n.d.–0.133 EE2. A relative high amount of EE2 was found in river Zala (0.68 ng/L) and in Hévíz-Páhoki canal (0.52 ng/L), which are both in the catchment area of Lake Balaton (Hungary).     

Critical evaluation of the measurement of the 1- octanol / water partition coefficient of hydrophobic compounds

Data on the experimental measurement of the octanol/water partition coefficient (K_ow) with hydrophobic compounds was assembled from the literature. The precision, characterised by the standard deviation of mean K_ow values based on five commonly used experimental methods, over an extended K_ow range was found to generally decline with compounds having log K_ow > 5.5. In the log K_ow range from 2.0 to 5.5 there was little difference between the mean values of log K_ow determined by the different methods but major differences occured with compounds having log K_ow > 5.5. The agreement between calculated ClogP values and K_ow values derived from individual experimental methods indicated that ClogP overestimates log K_ow from all experimental methods with compounds having values greater than 5.5.     

Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

Properties of the 2,3,7,8-TCDD receptor- a QSAR approach

The Ah or 2,3,7,8-TCDD receptor protein plays an important role in mediating the biologic, toxic and genotoxic effects of aryl and halogenated aryl hydrocarbons. An assessment of the physicochemical parameters which facilitate ligand: receptor interactions was determined by multiple parameter linear regression analysis of the relative receptor binding affinities of a series of 7-substituted-2,3-dichlorodibenzo-p-dixoins (Eq 1), 8-substituted-2,3-di (Eq. 2) and 2,3,4-trichlorodibenzofurans (Eq 3). The results demonstrate that substituent lipophilicity (π) and molecular volumes were

(Eq.1)

log (I/EC₅₀) = 1.24 π + 6.10

(Eq.2)

log (I/EC₅₀) = 1.10 π + 5.19

(Eq.3)

log (I/EC₅₀) = 1.09 π + 5.77

the major determinant factors governing interactions between the rat hepatic cytosolic receptor protein and the diverse substituted ligands. It has been shown that there are marked differences in species sensitivity to 2,3,7,8-TCDD (i.e. guinea pig > rat maice > hamster) although hepatic receptor levels in these species are comparable. QSAR analysis of the receptor binding EC₅₀ data for the 7-substituted-2,3-dichlorodibenzo-p-dioxins using rat (Eq. 1), mouse (Eq. 4), guinea pig (Eq. 5) and hamster (Eq. 6) hepatic cytosol demonstrated that there were significant differences in these equations. However it was also noted that

(Eq.4)

log (I/EC₅₀) = 0.95 + 0.93 E_s + 5.28

(Eq.5)

log (I/EC₅₀) = 0.94 + 0.579 σ_p + 6.13

(Eq.6)

log (I/EC₅₀) = 0.70 + 1.227 σ_p + 6.38

physicochemical factors which are important for ligand-receptor interactions were identical for the most sensitive (guinea pig) and least sensitive (hamster) species. These results indicate that events which follow the initial ligand-receptor interaction must be the major factors which determine species sensitivity to 2,3,7,8-TCDD.     

Population-level toxicity of the insecticide, spinosad and the nonylphenol polyethoxylate, R-11, to the cladoceran species Ceriodaphnia dubia Richard

The effects of the natural insecticide, spinosad, and the agricultural adjuvant, R-11, were evaluated on populations of the water flea, Ceriodaphnia dubia after chronic 8-day exposures. The number of individuals used to start the chronic exposure studies (founders) and the number of offspring/surviving female were significantly reduced after exposure to spinosad concentrations ≥ 2.5 μg/L. The final number of individuals was significantly reduced after exposure to spinosad concentrations ≥ 1.0 μg/L. Population growth rate was significantly reduced after exposure to spinosad concentrations ≥ 1 μg/L. Extinction occurred (defined as negative population growth rate) after exposure to spinosad concentrations of 10 μg/L. Therefore, negative effects were observed in C. dubia after exposure to spinosad at a concentration near the chronic expected environmental concentration (EEC) of 2.3 μg/L. R-11 was much less toxic to C. dubia than spinosad. The number of founders was not significantly reduced until C. dubia were exposed to 12,000 μg/L. The number of offspring/surviving female, final number of individuals, and population growth rate were significantly reduced after exposure to R-11 concentrations ≥ 5,000 μg/L. Extinction occurred after exposure to R-11 concentrations of 12,000 μg/L which was above the EEC of 790 μg/L. These results indicate that spinosad and R-11 both have lethal and sublethal effects on C. dubia. However, spinosad appears to affect C. dubia at or near the EEC while R-11 does not negatively affect this species until concentrations are much higher than the EEC.     

Contaminated sediments and bioassay responses of three macroinvertebrates, the midge larva Chironomus riparius, the water louse Asellus aquaticus and the mayfly nymph Ephoron virgo

Bioassays are widely used to estimate ecological risks of contaminated sediments. We compared the results of three whole sediment bioassays, using the midge larva Chironomus riparius, the water louse Asellus aquaticus, and the mayfly nymph Ephoron virgo. We used sediments from sixteen locations in the Dutch Rhine-Meuse Delta that differed in level of contamination. Previously developed protocols for each bioassay were followed, which differed in sediment pretreatment, replication, and food availability. The Chironomus bioassay was conducted in situ, whereas the other two were conducted in the laboratory. The measured endpoints, survival and growth, were related to contaminant levels in the sediment and to food quantity in water and sediment.

Only the response of A. aquaticus in the bioassay was correlated with sediment contamination. Food availability in overlying water was much more important for C. riparius and E. virgo, thereby masking potential sediment contaminant effects. We conclude that growth of A. aquaticus was depressed by sediment contamination, whereas growth of E. virgo and C. riparius was stimulated by seston food quantity. We discuss that the trophic state of the ecosystem largely affects the ecological risks of contaminated sediments.     

Pulsed discharge plasma induced Fenton-like reactions for the enhancement of the degradation of 4-chlorophenol in water

To sufficiently utilize chemically active species and enhance the degradation rate and removal efficiency of toxic and biorefractory organic pollutant para-chlorophenol (para-CP), the introductions of iron metal ions (Fe²⁺/Fe³⁺) into either pulsed discharge plasma (PDP) process or the PDP process with TiO₂ photo-catalyst were tentatively performed. The experimental results showed that under the same experimental condition, the degradation rate and removal efficiency of para-CP were greatly enhanced by the introduction of iron ions (Fe²⁺/Fe³⁺) into the PDP process. Moreover, when iron ions and TiO₂ were added together in the PDP process, the degradation rate and removal energy of para-CP further improved. The possible mechanism was discussed that the obvious promoting effects were attributed to ferrous ions via plasma induced Fenton-like reactions by UV light irradiation excited and hydrogen peroxide formed in pulsed electrical discharge, resulting in a larger amount of hydroxyl radicals produced from the residual hydrogen peroxide. In addition, the regeneration of ferric ions to ferrous ions facilitates the progress of plasma induced Fenton-like reactions by photo-catalytic reduction of UV light, photo-catalytic reduction on TiO₂ surface and electron transfer of quinone intermediates, i.e. 1,4-hydroquinone and 1,4-benzoquinone.     

An assessment of the risks associated with PCDDs and PCDFs following the application of sewage sludge to agricultural land in the UK

A model has been developed to describe the transfer of PCDDs and PCDFs from sludge-amended soils to the human foodchain. The model is conservative and assumes that all foods consumed by an individual are derived from sludge-amended soils. Predicted concentrations of PCDDs and PCDFs in potatoes, cereals, root vegetables and leafy vegetables were in close agreement with mean concentrations reported in the food survey conducted by MAFF in the UK. Predicted concentrations in milk were well below the Maximum Tolerable Concentration adopted by MAFF. Assuming a half-life of ten years in sludge-amended soils, the maximum estimated incremental daily intake (IDI) predicted by the model following ten applications of sludge to agricultural land was 0.80 pg I-TEQ kg⁻¹ day⁻¹, representing an increase of approximately 45% on current levels of background exposure. For an individual whose diet is solely derived from sludge-amended soils, the total exposure is predicted to be approximately 181 pg I-TEQ day⁻¹ or 2.6 pg I-TEQ kg⁻¹ day⁻¹. This compares with an average background exposure of approximately 2 pg I-TEQ kg⁻¹ day⁻¹, well within the TDI of 10 pg I-TEQ kg⁻¹ day⁻¹ and indicates that the application of sewage sludge to agricultural land under the conditions assumed would not appear to present a significant health risk under the conservative scenarios considered in this assessment.     

Concentrations and accumulation patterns of organochlorine contaminants in the blubber of harbour porpoises, Phocoena phocoena, from the coast of Newfoundland, the Gulf of St Lawrence and the Bay of Fundy/Gulf of Maine

Concentrations of 99 organochlorine compounds were measured in the blubber of 196 harbour porpoises, Phocoena phocoena, killed in commercial gill net fisheries in the western North Atlantic. PCBs and chlorinated bornanes (CHB) were the dominant contaminants in all porpoises. Mean concentrations (with standard deviations) of PCBs and CHBs from the three regions were as follows: Bay of Fundy/Gulf of Maine, PCB males 17.3 +/- 11.2 microg/g, PCB females 11.4 +/- 4.8 microg/g, CHB males 11.5 +/- 6.6 microg/g, CHB females 8.4 +/- 5.3 microg/g; Gulf of St Lawrence, PCB males 10.6 +/- 5.4 microg/g, PCB females 7.2 +/- 3.9 microg/g, CHB males 14.1 +/- 8.8 microg/g, CHB females 9.0 +/- 6.3 microg/g; southeast Newfoundland, PCB males 5.2 +/- 2.5 microg/g, PCB females 5.5 +/- 4.4 microg/g, CHB males 7.0 +/- 2.2 microg/g, CHB females 5.5 +/- 3.0 microg/g. The relative composition of the major contaminant groups found in male and female harbour porpoise blubber from the three locations varied. In order of decreasing concentration, porpoises from Fundy/Maine had PCBs > CHB > DDT > chlordanes (CHL), whereas Gulf of St Lawrence and Newfoundland porpoises had CHB > PCB > DDT > CHL. Significant increases with age were observed for most contaminants in male harbour porpoises, and significant decreases were observed in females. Females lose about 15% of their contaminant burden per birth. PCB and DDT levels in porpoises from the Bay of Fundy are significantly lower than those recorded in the 1970s.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

淀粉基黄原酸盐处理重金属废水的条件优化研究

采用淀粉基黄原酸盐处理含重金属的电镀废水 ,对淀粉基黄原酸盐的用量、pH值和反应时间等条件进行了研究。结果发现 ,1L含氰电镀废水 (含Cr3+15mg/L、Cu2 +3mg/L、Ni2 +9.2mg/L和Zn2 +6mg/L) ,加入 1g淀粉基黄原酸盐 ,调节 pH为 8,搅拌 1h ,过滤 ,处理后的废水中Cr3+、Cu2 +、Zn2 +和Ni2 +残余浓度分别为 0 .0 8mg/L、0 .0 1mg/L、0 .1mg/L和 0 .0 8mg/L。含有重金属盐的残渣 ,可用硝酸处理 ,以回收重金属     

Fe-exchanged zeolite as the effective heterogeneous Fenton-type catalyst for the organic pollutant minimization: UV irradiation assistance

The issue of investigations in this study was an application of heterogeneous Fenton-type catalyst, Fe-exchanged zeolite FeZSM5, for the minimization of phenol and overall organic content in the model wastewater. Applied treatment systems included variation of heterogeneous and homogeneous Fenton-type catalyst with and without the assistance of UV irradiation, FeZSM5/H2O2, Fe2+/H2O2/NH4ZSM5, Fe3+/H2O2/NH4ZSM5, UV/FeZSM5/H2O2, UV/Fe2+/H2O2/NH4ZSM5 and UV/Fe3+/H2O2/NH4ZSM5. Processes efficiency was evaluated on the basis of phenol removal, mineralization extent, H2O2 consumption and concentration of iron ions in the bulk after the treatment. By all applied systems, complete phenol removal was achieved in less than 30 min of treatment time. Systems including heterogeneous Fenton-type catalyst showed somewhat lower mineralization efficiency in comparison to the corresponding systems applying homogeneous Fenton-type catalysts and the addition of synthetic zeolite NH4ZSM5. Significantly lower concentration of iron ions in the bulk after the treatment could give these systems, particularly UV/FeZSM5/H2O2, a great advantage over the homogeneous Fenton-type systems.     

Identifying source regions for the atmospheric input of PCDD/Fs to the Baltic Sea

PCDD/F contamination of the Baltic Sea has resulted in the European Union imposing restrictions on the marketing of several fish species. Atmospheric deposition is the major source of PCDD/Fs to the Baltic Sea, and hence there is a need to identify the source regions of the PCDD/Fs in ambient air over the Baltic Sea. A novel monitoring strategy was employed to address this question. During the winter of 2006–2007 air samples were collected in Aspvreten (southern Sweden) and Pallas (northern Finland). Short sampling times (24 h) were employed and only samples with stable air mass back trajectories were selected for analysis of the 2,3,7,8-substituted PCDD/F congeners. The range in the PCDD/F concentrations from 40 samples collected at Aspvreten was a factor of almost 50 (range 0.6–29 fg TEQ/m³). When the samples were grouped according to air mass origin into seven compass sectors, the variability was much lower (typically less than a factor of 3). This indicates that air mass origin was the primary source of the variability. The contribution of each sector to the PCDD/F contamination over the Baltic Sea during the winter half year of 2006/2007 was calculated from the average PCDD/F concentration for each sector and the frequency with which the air over the Baltic Sea came from that sector. Air masses originating from the south–southwest, south–southeast and east segments contributed 65% of the PCDDs and 75% of the PCDFs. Strong correlations were obtained between the concentrations of most of the PCDD/F congeners and the concentration of soot. These correlations can be used to predict the PCDD/F concentrations during the winter half year from inexpensive soot measurements.     

On the performance of Fe and Fe,F doped Ti-Pt/PbO2 electrodes in the electrooxidation of the Blue Reactive 19 dye in simulated textile wastewater

The electrochemical performance of pure Ti–Pt/β-PbO₂ electrodes, or doped with Fe and F (together or separately), in the oxidation of simulated wastewaters containing the Blue Reactive 19 dye (BR-19), using a filter-press reactor, was investigated and then compared with that of a boron-doped diamond electrode supported on a niobium substrate (Nb/BDD). The electrooxidation of the dye simulated wastewater (volume of 0.1 l, with a BR-19 initial concentration of 25 mg l⁻¹) was carried out under the following conditions: current density of 50 mA cm⁻², volume flow rate of 2.4 l h⁻¹, temperature of 25 °C and electrode area of 5 cm². The performances of the electrodes in the dye decolorization were quite similar, achieving 100% decolorization, and in some cases 90% decolorization was achieved by applying only ca. 0.3 A h l⁻¹ (8 min of electrolysis). The reduction of the simulated wastewater organic load, monitored by its total organic carbon content (TOC), was greater for the Ti–Pt/β-PbO₂–Fe,F electrode obtained from an electrodeposition bath containing 1 mM Fe³⁺ and 30 mM F⁻. In this case, after 2 h of electrolysis the obtained TOC reduction was 95%, while for the pure β-PbO₂ and the Nb/BDD electrodes the reductions were 84% and 82%, respectively.     

Acute toxicity of the insect larvicide abate® (temephos) on the fish tilapia melanopleura and the dragonfly larvae neurocordelia virginiensis.

Abstract

Acute bioassay tests on the toxic effects of the insect larvicide Abate® (temephos) on the mouth brooder cichlid fish Tilapia melanopleum and the dragonfly larvae (Odonata) Neurocordulia virginiensis were conducted in static non renewal toxicity test set ups. The 96h‐LC50 (95% confidence intervals) was 30.2 (20.5‐ 44.20) mg/L for the fish and 2.0 (1.16–2.0) mg/L for the dragonfly larvae. The dragonfly larvae were 15 times more susceptible to the larvicide than the tilapia. The calculated NOEC (No Observable Effect Concentration) was 14.1 mg/L for the fishand less than 1.0 mg/L for the insect larvae. The estimated ‘safe’ concentration of the pesticide to the fish was 3.0 mg/L and 0.2 mg/L for insect larvae. These figures are far above the concentrations approved for use in the control of mosquito larvae(0.0004–0.01 mg/L). It appears that the application of toxic levels of the insecticide for the elimination of some aquatic invertebrates may be ‘safe’ for normal survival, growth and reproduction offish and some aquatic insect larvae.     

Studies on the mechanism of PCDD/PCDF formation during the bleaching of pulp

Laboratory bleaching experiments were performed to investigate PCDD/PCDF formation mechanisms. The results indicated that there were two (or more) mechanisms; direct chlorination of DBD/DBF and formation from precursors which are not extractable. In general, PCDDs/PCDFs are formed in the C stage but some minor isomers were found to be formed in the E stage.