Preferential sorption of some natural organic matter fractions to titanium dioxide nanoparticles: influence of pH and ionic strength

Natural organic matter (NOM) sorption to nanoparticles (NPs) can influence their transport and bioavailability in the aquatic environment. The sorption affinity of NOM to surfaces including NPs is size dependent, and depending on environmental conditions, NOM may enhance or mitigate NPs toxicity. The aim of this study was to investigate the preferential sorption of different-sized fractions of NOM to titanium dioxide (TiO₂) NPs. We specifically investigated the influence of pH, ionic strength, and NOM concentration on the extent of this preferential sorption using a constant sorbent concentration (400 mg/L TiO₂ NPs). Additionally, sorption of NOM to TiO₂ NPs at varying pH was investigated. The nonsorbed NOM was separated from the sorbed, by 50 nm polycarbonate membrane filters and ultracentrifugation. High-performance size exclusion chromatography (HPSEC) was used to determine the average molecular weights of NOM (MWw). Corroborative evidence of preferential sorption of different-sized molecular weight fractions of NOM was obtained from optical techniques such as absorbance and fluorescence spectrophotometry. The total organic carbon was measured by the Total Organic Carbon Analyzer—Shimadzu (TOC-VCPH). The results indicated that there is preferential sorption of larger sized fractions of NOM to TiO₂ NPs irrespective of NOM concentration. It was observed that the sorption of larger sized fractions of NOM was much enhanced at lower pH and at higher ionic strength. Both absorbance and fluorescence spectrophotometric techniques gave credible corroborative evidence on the extent of preferential sorption of lager sized fractions of NOM with respect to pH and ionic strength. The sorption results demonstrated higher sorption at lower pH than at higher pH. Overall, the results of this study suggest that the environmental conditions are key factors that can contribute to NOM’s fractional preferential sorption to NPs in the aquatic environment.     

Some Advances in Fluorometric Techniques for Water Tracing

A common technique for ground water tracing uses continuous or discrete analysis of fluorescent tracer dyes to produce tracer breakthrough curves which can be analysed to determine ground water trajectory, velocity and dispersivity. Some fluorescent dyes are excellent tracers, but there remain significant constraints in fluorometry with respect to installation, control and data acquisition using standard filter fluorometers as well as with general analytical protocols. This paper identifies some of the constraints associated with the widely used Turner Designs Model 10 Series filter fluorometer and technical and operational solutions which can significantly improve the precision, accuracy and time resolution of tracer data.     

Study of the relationships between bone lead levels and its variation with time and the cumulative blood lead index, in a repeated bone lead survey

The study aims were to: (i) investigate long term human lead metabolism by measuring the change of lead concentration in the tibia and calcaneus; and (ii) assess whether improved industrial hygiene was resulting in a slow accumulation of lead in an exposed workforce. 109Cd excited K X-ray fluorescence was used to measure tibia lead and calcaneus lead concentrations in 101 workers in a secondary lead smelter. 51 subjects had had similar bone lead measurements 5 years previously. Most of the other subjects had been hired since the first survey. Measurements of whole blood lead were available for the large majority of subjects. Tibia lead concentrations fell significantly (p<0.001) in the 51 subjects with repeated bone lead measurements, from a mean of 39 microg Pb (g bone mineral)(-1) to 33 microg Pb (g bone mineral)(-1). The change correlated negatively with the initial tibia lead concentration, producing an estimate for an overall half-life of 15 years, with a 95% confidence interval of 9 to 55 years. Adding continuing lead exposure and recirculation of bone lead stores to the regression models produced half-life estimates of 12 and 9 years, respectively, for release of lead from the tibia. The repeat subjects showed no net change in calcaneus lead (64 microg Pb (g bone mineral)(-1) initially, 65 microg Pb (g bone mineral)(-1) 5 years later). Subjects not measured previously had average lead concentrations of 15 microg Pb (g bone mincral)(-1) in the tibia and 13 microg Pb (g bone mineral)(-1) in the calcaneus. The rate of clearance of lead from the tibia (9 to 15 years) is towards the more rapid end of previous estimates. The lack of a significant fall in the calcaneus lead was surprising. Attempts should be made to repeat this observation. If confirmed, it would have implications for models of lead metabolism. The relatively low lead concentrations in the non-repeat subjects are reassuring. However, observation after a longer period of employment would be desirable.     

Recycling of petroleum-contaminated sand

The environmental impact of using petroleum-contaminated sand (PCS) as a substitute in asphalt paving mixtures was examined. An appreciable component of PCS is oily sludge, which is found as the dregs in oil storage tanks and is also produced as a result of oil spills on clean sand. The current method for the disposal of oily sludge is land farming. However, this method has not been successful as an oil content of < 1% w/w is required, and difficulty was encountered in reaching this target. The reuse of the sludge in asphalt paving mixtures was therefore considered as an alternative. Standard tests and environmental studies were conducted to establish the integrity of the materials containing the recycled sludge. These included physical and chemical characterization of the sludge itself, and an assessment of the mechanical properties of materials containing 0%, 5%, 22% and 50% oily sludge. The blended mixtures were subjected to special tests, such as Marshall testing and the determination of stability and flow properties. The experimental results indicated that mixtures containing up to 22% oily sludge could meet the necessary criteria for a specific asphalt concrete wearing course or bituminous base course. To maximize the assay from the recycled material, the environmental assessment was restricted to the 50% oily sludge mixture. Leachates associated with this particular mixture were assayed for total organic residue and certain hazardous metal contaminants. The results revealed that the organics were negligible, and the concentrations of the metals were not significant. Thus, no adverse environmental impact should be anticipated from the use of the recycled product. Our research showed that the disposal of oily sludge in asphalt paving mixtures could possibly yield considerable savings per tonne of asphalt concrete, and concurrently minimize any direct impact on the environment.     

Route of egg yolk protein uptake in the oocytes of kuruma prawn,Penaeus japonicus

The route of egg yolk protein uptake into the oocytes of kuruma prawn, Penaeus japonicus, was studied using immunohistochemical and electron microscopical methods. Although a significant immunofluorescence with anti-vitellin-immunoglobulin was observed in the enlarged follicle cells surrounding oil globule stage oocytes of the early vitellogenic ovary, no fluorescence was detected in shrunken follicle cells surrounding oocytes in the yolk granule stage. Electron microscopically, yolk granule stage oocytes have an irregular surface with numerous well-developed microvilli. In contrast, the surface of follicle cells is relatively smooth. The irregular surface of yolk granule stage oocytes was covered with a layer of electron dense material. Similar dense material was found in the spaces between the neighboring follicle cells on the yolk granule stage oocytes. The outer surface of the follicle cells on yolk granule stage oocytes was covered by dense materials which were similar to those found on the irregular surface of oocytes. Micropinocytotic vesicles containing dense material were found in the ooplasm near the irregular surface with numerous well-developed microvilli. Dense material was concentrated in the peripheral part of the small forming yolk bodies of yolk granule stage oocytes. This suggests that the electron dense material, probably egg yolk protein, transferred to the surface of yolk granule stage oocytes from the spaces between the neighboring follicle cells may be incorporated into the ooplasm by pinocytosis through the microvilli and subsequently aggregate to form yolk bodies.     

Metal pollution assessment of sediment and water in the Shur River

Intensified industrialization and human activities have resulted in the release of various contaminants into the environment. Among them, heavy metals are often present as a result of mining, milling and industrial manufacturing. In the present investigation, bulk concentrations Pb, Cd, Zn, Cu, Fe, Ca and Al in Shur River (Iran) bed sediments and water around the Sarcheshmeh copper mine were measured from several sample locations. In addition, partitioning was assessed to determine the proportions of metals in different forms. The degree of sediment contamination was evaluated using an Enrichment Factor (EF) and geo-accumulation index (I (geo)) and a newly developed pollution index (I (POLL)). Elevated metals in sediment and water were found to be correlated with areas of the river that were proximal to direct and indirect mining activities. Cadmium and Zn showed the highest pollution index. Cluster analysis was performed in order to assess heavy metal interactions between water and sediment. Chemical partitioning studies revealed that organic metallic bonds were not significantly present in the sediment of the Shur River.     

An Experimental Methodology for Monitoring Contaminant Transport Through Geotechnical Centrifuge Models

In this paper, an attempt has been made to highlight an experimental methodology for monitoring contaminant transport through locally available silty soil and commercially available clay in geotechnical centrifuge models, for different compaction states. Use of multiple depth sensors to determine depth distribution of sodium chloride in the soil column has been detailed. The obtained results have been compared with argentometric method. To validate the centrifuge modelling, modelling of models has been used. The test setup developed can simulate contaminant transport mechanisms through the soil mass, which is approximately 10 m deep, over a period of 600 days. R _e and P _e are found to be N times higher in the centrifuge models. These numbers are found to be several orders less than unity. This indicates that laminar flow prevails and the dominating Cl⁻ transport mechanism in centrifuge is diffusion. The study also highlights the fact that the geotechnical centrifuge modelling can be used as a viable alternative to field scale experimentation.     

An assessment of the bioavailability of persistent organic pollutants from contaminated soil

A procedure to assess the bioavailability of persistent organic pollutants (POPs) from soil samples has been developed. The procedure is based on the use of simulated in vitro gastrointestinal extraction to remove POPs from soil matrices. The level of recovery, using this approach, is assessed following liquid-liquid extraction (LLE) and analysis by gas chromatography-mass selective detection (GC-MSD). The remaining soil residue is then extracted using pressurised fluid extraction (PFE) followed by GC-MSD analysis to assess the residual fraction. The residual fraction is monitored to determine the unavailable fraction i.e. not available for absorption in the gastrointestinal tract of humans. The procedure was applied to four soil samples i.e. an aged, spiked soil and three certified reference materials (CRMs) contaminated with POPs. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II), phenols (cresol, TCP and PCP), and base neutral compounds (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from aged, spiked soil following extraction with gastric fluid ranged from 0.8 to 8.3% while following intestinal extraction ranged from 5.5 to 13.5%, irrespective of POP. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II) from CRM 805-050 following extraction with gastric fluid were below the limit of detection while following intestinal extraction ranged from 5.3 to 12.8%. Recoveries of phenols (cresol, TCP and PCP) from CRM 401-225 following extraction with gastric fluid ranged from 1.6 to 2.0% while following intestinal extraction ranged from 4.1 to 5.4%. Recoveries of base neutral acid analytes (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from CRM 107-100 following extraction with gastric fluid ranged from 1.4 to 4.0% while following intestinal extraction ranged from 6.6 to 12.7%. It has been found that the majority of POPs present i.e. >75%, would be excreted if consumed and not be absorbed in the gastrointestinal tract of humans.