Two-site kinetic modeling of bacteriophages transport through columns of saturated dune sand

Breakthrough curves, on a semi-log scale, from tests in porous media with block-input of viruses, bacteria, protozoa and colloidal particles often exhibit a typical skewness: a rather slowly rising limb and a smooth transition of a declining limb to a very long tail. One-site kinetic models fail to fit the rising and declining limbs together with the tail satisfactorily. Inclusion of an equilibrium adsorption site does not seem to improve simulation results. This was encountered in the simulation of breakthrough curves from a recent field study on the removal of bacteriophages MS2 and PRD1 by passage through dune sand. In the present study, results of laboratory experiments for the study of this issue are presented. Breakthrough curves of salt and bacteriophages MS2, PRDI, and phiX174 in 1 D column experiments have been measured. One- and two-site kinetic models have been applied to fit and predict breakthrough curves from column experiments. The two-site model fitted all breakthrough curves very satisfactorily, accounting for the skewness of the rising limb as well as for the smooth transition of the declining limb to the tail of the breakthrough curve. The one-site model does not follow the curvature of the breakthrough tail, leading to an overestimation of the inactivation rate coefficient for attached viruses. Interaction with kinetic site 1 is characterized by relatively fast attachment and slow detachment, whereas attachment to and detachment from kinetic site 2 is fast. Inactivation of viruses and interaction with kinetic site 2 provide only a minor contribution to removal. Virus removal is mainly determined by the attachment to site 1. Bacteriophage phiX174 attached more than MS2 and PRD1, which can be explained by the greater electrostatic repulsion that MS2 and PRD1 experience compared to the less negatively charged phiX174.     

The use of XAD-resins for the detection of mutagenic activity in water: I. Studies with surface water

A study of the effects of different XAD-resins, bed volume, flow rate, pH and type of eluent on the extraction of organic mutagens from surface water is presented. XAD-4/8 is as effective as XAD-2 in concentrating organic mutagens from surface water and dimethylsulfoxide (DMSO) is as efficient as acetone in eluting the adsorbed organic mutagens. The latter allows direct testing up to 0.5 ml of DMSO concentrate in the Ames test. Variation of the pH of the water after passing the XAD-4/8, followed by readsorption, shows that the majority of the mutagenic activity due to dissolved organics is adsorbed at neutral pH. Only a minor fraction is readsorbed at pH 3. Further a XAD-4/8 concentrate and a similar concentrate prepared by freeze drying gives similar mutagenic activity. This indicates that many of the organic mutagens are recovered in the XAD-4/8 concentrate.It is concluded that adsorption on XAD-4/8, followed by direct testing of the DMSO eluates in the Ames test, presents a rapid and relatively simple way to detect low concentrations of organic mutagens in surface water. The general suitability of the method is shown for different types of surface water.     

Analysis of heavy metal distribution in superficial estuarine sediments (estuary of Bilbao, Basque Country) by open-focused microwave-assisted extraction and ICP-OES

Open-focused microwave-assisted extraction and ICP-OES determination of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn from surface sediments of the estuary of Bilbao (Basque Country, North of Spain) was carried out. All the samples were collected at three different tributaries of the estuary (Asua, Galindo and Nerbioi-Ibaizabal) every two months during 1999. The digestion procedure was proposed from the conclusions of a fractionated factorial design, and the precision and accuracy of the method was verified using a certified reference sediment (RTC008-050). The results of the analysis were statistically treated by means of principal component analysis and correlation analysis. The principal component analysis of sediment data (32 samples × 9 metals) indicated different patterns of contamination regarding the tributary and sampling station. The two main patterns observed were a steady increment of the metal concentration along all the campaigns in the samples collected in the Galindo River and a seasonal variation in the Nerbioi-Ibaizabal River, with higher metallic content during summertime and lower content during wintertime.     

Evaluation of relative photonic efficiency in heterogeneous photocatalytic reactors

The evaluation of photonic efficiency in heterogeneous photocatalysis remains elusive because the number of absorbed photons is difficult to assess experimentally. The photonic efficiency of heterogeneous photocatalytic reactors depends on the reactor geometry, irradiation source, and photocatalyst properties. In this work, the relative photonic efficiency of heterogeneous photocatalytic reactors to degrade an azo dye was evaluated using phenol as the standard system. The experimental tests were carried out in a batch reactor under different conditions of pH, catalyst dosage, initial concentration, and ultraviolet (UV) lamps. The kinetics of disappearance of both phenol and azo dye were studied using the initial rate method and were described according to the Langmuir-Hinshelwood (L-H) kinetic model. It was observed that the relative photonic efficiency depends on the adsorption/desorption properties of the photocatalyst.     

Irrigation runoff insecticide pollution of rivers in the Imperial Valley, California (USA)

The Alamo and New Rivers located in the Imperial Valley, California receive large volumes of irrigation runoff and discharge into the ecologically sensitive Salton Sea. Between 1993 and 2002 we conducted a series of studies to assess water quality using three aquatic species: a cladoceran (Ceriodaphnia dubia), a mysid (Neomysis mercedis), and a larval fish (Pimephales promelas). Although no mortality was observed with the P. promelas, high-level toxicity to the invertebrate species was documented in samples from both rivers during many months of each year. Toxicity identifications and chemical analyses identified the organophosphorus insecticides (OP), chlorpyrifos and diazinon, as the cause of C. dubia toxicity. The extent of the C. dubia mortality was highly correlated with quantities of these OPs applied in the river watersheds. C. dubia mortality occurred during more months of our 2001/2002 study than in the 1990s investigations. During 2001/2002, the extensive C. dubia mortality observed in New River samples was caused by OP insecticide pollution that originated from Mexico. Mortality to N. mercedis in New River samples was likely caused by contaminants other than OP insecticides. Our studies document OP insecticide-caused pollution of the Alamo River over a 10-year period and provide the necessary information for remediation efforts.     

Significance of platinum group metals emitted from automobile exhaust gas converters for the biosphere

Intention, Goal, Scope, Background  Following the introduction of automobile catalytic converters the platinum group metals (PGM) platinum (Pt), palladium (Pd) and rhodium (Rh) gain on increasing interest in environmental research as these metals are emitted with exhaust fumes into the environment. Consequently, elevated PGM levels were found in different environmental matrices uch as road dusts, soils along heavily frequented roads, sediments of urban rivers etc. Accordingly, the effects of increasing PGM emissions on the biosphere are controversially discussed. Objective  This paper summarizes the present knowledge on the biological availability of PGM to plants and animals. As biological availability is one of the most decisive factors determining the toxicologi-cal potential of xenobiotics, this information is very important to evaluate the possible threat of the noble metals to ecosystems. Results and Discussion  The availability of soluble as well as particle bound PGM to terrestrial plants was demonstrated in several studies. Experimental investigations revealed uptake of Pt, Pd and Rh also by aquatic plants. Additionally, the biological availability of the noble metals for animals has been verified in experimental studies using soluble metal salts, catalytic converter model substances, sediments of urban rivers, road dust or tunnel dust as metal sources. These studies refer mainly to aquatic animals. Beside of free living organisms, in particular worms parasitizing fish demonstrated a high potential to accumulate PGM. This could be of great interest in respect of biomonitoring purposes. Generally, for plants as well as for animals Pd turns out to be the best available metal among the PGM. Compared to other heavy metals, the biological availability of PGM from road dust to zebra mussels(Dreissena polymorpha) ranged between that of Cd and Pb. Conclusion  Especially chronic effects of PGM on the biosphere can not be excluded due to (1) their cumulative increase in the environment, (2) their unexpected high biological availability and bioaccumulation and (3) their unknown toxicological and ecotoxicological potential. However, it appears that acute effects on ecosystems due to anthropogenic PGM emission are not likely. Recommendation and Outlook  Research on environmental PGM contamination of the biosphere, especially the fauna, and on long-term toxiciry of low PGM concentrations is highly appreciated. These studies require very sensitive analytical techniques to determine PGM even in low sample amounts. Research has to be done in particular on reliable determination of (ultra) trace levels of Pd and Rh as the lack of data on these two metals is mainly due to analytical problems.     

Ligand exchange rate of metal-nom complexes by EDTA

Metal complexation by natural ligands is important for metal transport and distribution in surface and ground water. The goal of the work was to study the ligand exchange rate for two important metal ions in natural aquatic systems (Al, Fe) was determined using EDTA and natural organic matter (NOM) of humic type as ligands. After adding EDTA to a solution containing metal-NOM complexes, these complexes dissociated and metal-EDTA complexes were formed. Metal-NOM complexes were separated from metal-EDTA complexes with the help of size-exclusion chromatography and detected by on-line inductively coupled plasma-mass spectrometry (ICP-MS). Injecting the samples into the system over time after addition of EDTA allowed us to measure the rate of the exchange of NOM by EDTA. The experiments could be well described with a first-order rate law assuming that the dissociation of the metal-NOM complexes is the rate-determining step. The exchange rate of Fe was found to be faster than that of Al. This corresponds well with the exchange rate of water molecules from the coordination sphere of the metal ions, which is also faster for Fe than for Al. Furthermore, the UV and the fluorescence signal of the chromatograms were measured. The results indicate that no disaggregation of NOM molecules took place, although about 75-85% of the aggregate-forming metal ions exchanged NOM by EDTA in their coordination sphere. This suggests clearly the fundamental role of NOM in colloidal transport of metals and in their bioavailability.     

Environmental impact and recovery at two dumping sites for dredged material in the North Sea

The environmental impact and recovery associated with the long and uninterrupted disposal of large volumes of moderately contaminated dredged material from the port of Rotterdam was studied at nearby dumping sites in the North Sea. Observations were made on sediment contamination, ecotoxicity, biomarker responses and benthic community changes shortly after dumping at the 'North' site had ceased and at the start of disposal at the new dumping site 'Northwest'. During the period of dumping, very few benthic invertebrates were found at the North site. Concentrations of cadmium, mercury, polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs) and tributyltin (TBT) in the fine sediment fraction (<63 microm) from this site were 2-3 times higher than at the reference site. In four different bioassays with marine invertebrates the sediments showed no acute toxic effects. In tissue (pyloric caeca) of resident starfish Asterias rubens, residual levels of mercury, zinc, PCBs and dioxin-like activity were never more than twice those at the reference site. Four different biomarkers (DNA integrity, cytochrome P450 content, benzo[a]pyrene hydroxylase activity and acetylcholinesterase inhibition) were used on the starfish tissues, but no significant differences were found between North and the reference site. Minor pathological effects were observed in resident dab Limanda limanda. One year after dumping had ceased at the North site, a significant increase in the species richness and abundance of benthic invertebrates and a concomitant decrease in the fine sediment fraction of the seabed were observed. After 8.2 million m3 of moderately contaminated dredged material had been dumped at the new dumping site Northwest, the species richness and abundance of benthic invertebrates declined over an area extending about 1-2 km eastwards. This correlated with a shift in sediment texture from sand to silt. The contamination of the fine sediment fraction at the Northwest location doubled. It is concluded that marine benthic resources at and around the dumping sites have been adversely affected by physical disturbance (burial, smothering). However, no causal link could be established with sediment-associated contaminants from the dredged spoils.     

Evaluation of EU risk assessments existing chemicals (EC Regulation 793/93)

An evaluation was performed on the first group (41) of completed risk assessments for chemicals of the EU priority lists (Existing Chemicals; EC Regulation 793/93). The evaluation focussed on the conclusions of the risk assessments. The EU risk assessment process detected a high number of substances of concern. Furthermore priority chemicals may pose potential risks to the whole range of protection goals of the risk assessment. The predictability of the risk assessments for priority chemicals was investigated. Our a priori knowledge on possible risks of priority chemicals is found to be poor, especially for consumers. Both for environment and human health the potential risks were linked with a broad spectrum of use patterns. It is concluded that no industry category can in advance be excluded from performing risk assessments. For a great number of chemicals, additional testing was found to be needed to finalize the risk assessment. This evokes questions about the completeness of the current base-set, but also about the suitability of some of the submitted human health tests that should initially fulfil the base-set needs. The results of this evaluation are useful for ongoing discussions on risk assessment processes for chemicals.     

Monitoring of polychlorinated biphenyls in Belgian human adipose tissue samples

Polychlorinated biphenyls (PCBs) were monitored in Belgian human adipose tissue samples from deceased individuals (n=100). Their mean age was 52, ranging from 2 to 91 years. There were 57 men and 43 women. Other known variables were date of autopsy and place of residence. No information about diet or occupation was available. The seven marker congeners PCB 28, 52, 101, 118, 138, 153 and 180 were analysed in the samples with a GC-MS/MS method validated according to Commission Decision 2002/657/EC. Extracted fat was cleaned-up over a glass column filled with n-hexane, acid silica, deactivated alumina and anhydrous sodium sulfate. The whole procedure was subjected to a rigorous quality control programme with retention times, ion chromatograms and intensity ratios of the monitored product ions as identification criteria. The total PCB concentration ranged between 10 and 1640 ng g-1 fat, with a mean value of 658 ng g-1 fat. In the age groups of 0-9 (n=1), 10-19 (n=4), 20-29 (n=11), 30-39 (n=13), 40-49 (n=15), 50-59 (n=14), 60-69 (n=14), 70-79 (n=20), 80-89 (n=6) and 90-99 (n=2), the mean total PCB concentrations were 10, 134, 253, 445, 557, 687, 807, 962, 959, and 1191 ng g-1 fat, respectively. So, there was an increase of PCB body burden with age. For the male subjects (n=57; mean age of 53) the mean total PCB concentration was 633 ng g-1 fat. For the female subjects (n=43; mean age of 52) it was 690 ng g-1 fat. There was no significant sex-related difference in the concentrations of marker PCBs.