Predicted concentrations of biocides from antifouling paints in Visakhapatnam Harbour

The concentrations of biocides leached from antifouling coatings are monitored in most of the developed countries. However, in India and many other developing countries, there is very little data available on the concentrations of biocides in ports and harbours. The first step was to obtain the order of magnitude levels of concentrations of biocides in the marine environment of the Visakhapatnam Harbour, and the MAM-PEC (Marine Antifoulant Model to Predict Environmental Concentrations) model was used to predict these values. The Visakhapatnam Port lies on the eastern coast of India, roughly halfway between Chennai and Kolkata, and is the largest port in India. This port is a natural harbour; the long and narrow outlet to the open sea makes it a 'poorly flushed' harbour. Predicted concentrations of tributyltin (TBT), copper, dichlofluanid, seanine, irgarol, diuron, tolylfluanid, and zinc pyrithione were computed. The results of the computations indicate that the levels of these biocides are comparable to those in many western countries. This gives credence to the fact that persistence of TBT and some other biocides is a global problem that cannot be ignored.     

Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

Elucidation of lead-induced oxidative stress in Talinum triangulare roots by analysis of antioxidant responses and DNA damage at cellular level

Hydroponic experiments were performed with Talinum triangulare (Jacq.) Willd. focusing the root cellular biochemistry with special emphasis on DNA damage, structural, and elemental analyses in Pb(NO₃)₂ exposed with 0, 0.25, 0.5, 0.75, 1.0, and 1.25 mM for 7 days. Lead (Pb) increased reactive oxygen species production, lipid peroxidation, protein oxidation, cell death, and DNA damage and decreased the protein content in a dose-dependent manner. Likewise, a dose-dependent induction of antioxidative enzymes superoxide dismutase and catalase by Pb was evident. Ascorbate peroxidase on the other hand responded biphasically to Pb treatments by showing induction at low (0.25 and 0.50) and repression at high (0.75–1.25 mM) concentrations. The estimation of proline content also indicated a similar biphasic trend. Scanning electron microscope and energy-dispersive X-ray spectroscopy analysis showed that 1.25 mM Pb treatment resulted in ultrastructural modifications in roots and stem tissue that was marked by the change in the elemental profile. The findings pointed to the role of oxidative stress in the underlying Pb phytotoxicity and genotoxicity in T. triangulare.     

Fungicidal values of bio-oils and their lignin-rich fractions obtained from wood/bark fast pyrolysis

Pine wood, pine bark, oak wood and oak bark were pyrolyzed in an auger reactor. A total of 16 bio-oils or pyrolytic oils were generated at different temperatures and residence times. Two additional pine bio-oils were produced at the National Renewable Energy Laboratory in a fluidized-bed reactor at different temperatures. All these bio-oils were fractionated to obtain lignin-rich fractions which consist mainly of phenols and neutrals. The pyrolytic lignin-rich fractions were obtained by liquid-liquid extraction. Whole bio-oils and their lignin-rich fractions were studied as potential environmentally benign wood preservatives to replace metal-based CCA and copper systems that have raised environmental concerns. Each bio-oil and several lignin-rich fractions were tested for antifungal properties. Soil block tests were conducted using one brown-rot fungus (Gloeophyllum trabeum) and one white-rot fungus (Trametes versicolor). The lignin-rich fractions showed greater fungal inhibition than whole bio-oils for a impregnation solution 10% concentration level. Water repellence tests were also performed to study wood wafer swelling behavior before and after bio-oil and lignin-rich fraction treatments. In this case, bio-oil fractions did not exhibit higher water repellency than whole bio-oils. Comparison of raw bio-oils in soil block tests, with unleached wafers, at 10% and 25% bio-oil impregnation solution concentration levels showed excellent wood preservation properties at the 25% level. The good performance of raw bio-oils at higher loading levels suggests that fractionation to generate lignin-rich fractions is unnecessary. At this more effective 25% loading level in general, the raw bio-oils performed similarly. Prevention of leaching is critically important for both raw bio-oils and their fractions to provide decay resistance. Initial tests of a polymerization chemical to prevent leaching showed some success.     

A rapid spectrophotometric determination of persulfate anion in ISCO

Due to a gradual increase in the use of persulfate as an in situ chemical oxidation (ISCO) oxidant, a simple measurement of persulfate concentration is desirable to analyze persulfate distribution at designated time intervals on/off a site. Such a distribution helps evaluate efficacy of ISCO treatment at a site. This work proposes a spectrophotometric determination of persulfate based on modification of the iodometric titration method. The analysis of absorption spectra of a yellow color solution resulting from the reaction of persulfate and iodide in the presence of sodium bicarbonate reveals an absorbance at 352 nm, without significant interferences from the reagent matrix. The calibration graph was linear in the range of persulfate solution concentration of 0-70 mM at 352 nm. The proposed method is validated by the iodometric titration method. The solution pH was at near neutral and the presence of iron activator does not interfere with the absorption measurement. Also, analysis of persulfate in a groundwater sample using the proposed method indicates a good agreement with measurements by the titration method. This proposed spectrophotometric quantification of persulfate provides a simple and rapid method for evaluation of ISCO effectiveness at a remediation site.     

Metal fractionation study on bed sediments of Hussainsagar Lake, Hyderabad, India

Hussainsagar Lake in the heart of Hyderabad City (India) receives toxic substances through five streams draining from a catchment area of 245 km². Of particular interest are heavy metals received from urban runoff as well as municipal sewage and industrial effluents. Heavy metals entering the lake get adsorbed onto the suspended sediments, which eventually settle down in the bottom of the lake. In this study, fractionation of metal ions has been studied on the bed sediments of Hussainsagar Lake in order to determine the ecotoxic potential of metal ions. Comparison of sediments with average shale values indicated anthropogenic enrichment with copper, nickel, lead, cadmium, and zinc. The risk assessment code as applied to the present study reveals that 10–17% of manganese, 10–18% of nickel, 14–24% of chromium, 10–19% of lead, 21–30% of cadmium, and 18–28% of zinc exist in exchangeable fraction and, therefore, comes under medium risk category and may enter into food chain. The association of these metals with the exchangeable fraction may cause deleterious effects to aquatic life. The present database will help in formulating guidelines for carrying out dredging operations under restoration programs in the Hussainsagar Lake.     

Multiresidue analysis of neonicotinoids by solid-phase extraction technique using high-performance liquid chromatography

For routine monitoring of pesticides, a multiresidue analysis through solid-phase extraction technique and using high-performance liquid chromatography (HPLC) in cotton seed cake (CSC) has been developed. Extraction of fortified samples was carried out with aqueous acetone under vacuum. The concentrated extract was loaded onto the solid-phase extraction units, preconditioned with acetonitrile. The extraction units were then washed with hexane and finally eluted with acetonitrile. The pesticide residues were determined using a multiresidue method by reversed-phase HPLC. The average percentage recoveries were found to range between 65.47% and 110% at spiking levels of 10 to 40 mg/kg. The method developed shows a healthy rate of recovery and can successfully be utilized for the extraction and screening of neonicotinoid residues in CSC. The detection limits for imidacloprid, acetamiprid, and thiacloprid using this method were found to be 5, 10, and 20 mg/kg, respectively.     

Soil contamination of heavy metals in the Katedan Industrial Development Area, Hyderabad, India

Studies on quantitative soil contamination due to heavy metals were carried out in Katedan Industrial Development Area (KIDA), south of Hyderabad, Andhra Pradesh, India under the Indo-Norwegian Institutional Cooperation Programme. The study area falls under a semi-arid type of climate and consists of granites and pegmatite of igneous origin belonging to the Archaean age. There are about 300 industries dealing with dyeing, edible oil production, battery manufacturing, metal plating, chemicals, etc. Most of the industries discharge their untreated effluents either on open land or into ditches. Solid waste from industries is randomly dumped along roads and open grounds. Soil samples were collected throughout the industrial area and from downstream residential areas and were analysed by X-ray Fluorescence Spectrometer for fourteen trace metals and ten major oxides. The analytical data shows very high concentrations of lead, chromium, nickel, zinc, arsenic and cadmium through out the industrial area. The random dumping of hazardous waste in the industrial area could be the main cause of the soil contamination spreading by rainwater and wind. In the residential areas the local dumping is expected to be the main source as it is difficult to foresee that rain and wind can transport the contaminants from the industrial area. If emission to air by the smokestacks is significant, this may contribute to considerable spreading of contaminants like As, Cd and Pb throughout the area. A comparison of the results with the Canadian Soil Quality Guidelines (SQGL) show that most of the industrial area is heavily contaminated by As, Pb and Zn and local areas by Cr, Cu and Ni. The residential area is also contaminated by As and some small areas by Cr, Cu, Pb and Zn. The Cd contamination is detected over large area but it is not exceeding the SQGL value. Natural background values of As and Cr exceed the SQGL values and contribute significantly to the contamination in the residential area. However, the availability is considerably less than anthropogenic contaminants and must therefore be assessed differently. The pre- and post-monsoon sampling over two hydrological cycles in 2002 and 2003 indicate that the As, Cd and Pb contaminants are more mobile and may expect to reach the groundwater. The other contaminants seem to be much more stable. The contamination is especially serious in the industrial area as it is housing a large permanent residing population. The study not only aims at determining the natural background levels of trace elements as a guide for future pollution monitoring but also focuses on the pollution vulnerability of the watershed. A plan of action for remediation is recommended.     

Assessment of drinking water quality using ICP-MS and microbiological methods in the Bholakpur area,Hyderabad, India

A total of 16 people died and over 500 people were hospitalized due to diarrhoeal illness in the Bholakpur area of Hyderabad, India on 6th May 2009. A study was conducted with immediate effect to evaluate the quality of municipal tap water of the Bholakpur locality. The study consists of the determination of physico-chemical properties, trace metals, heavy metals, rare earth elements and microbiological quality of drinking water. The data showed the variation of the investigated parameters in samples as follows: pH 7.14 to 8.72, EC 455 to 769 μS/cm, TDS 303.51 to 515.23 ppm and DO 1.01 to 6.83 mg/L which are within WHO guidelines for drinking water quality. The water samples were analyzed for 27 elements (Li, Be, B, Na, Mg, Al, Si, K, Ca, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Ba and Pb) using inductively coupled plasma-mass spectrometry (ICP-MS). The concentrations of Fe (0.12 to 1.13 mg/L), Pb (0.01 to 0.07 mg/L), Cu (0.01 to 0.19 mg/L), Ni (0.01 to 0.15 mg/L), Al (0.16 to 0.49 mg/L), and Na (38.36 to 68.69 mg/L) were obtained, which exceed the permissible limits of the World Health Organization (WHO) for drinking water quality guidelines. The remaining elements were within the permissible limits. The microbiological quality of water was tested using standard plate count, membrane filtration technique, thermotolerant coliform (TTC), and most probable number (MPN) methods. The total heterotrophic bacteria ranged from 1.0 × 10⁵ to 18 × 10⁷ cfu/ml. Total viable bacteria in all the water samples were found to be too numerable to count and total number of coliform bacteria in all water samples were found to be of order of 1,100 to >2,400 MPN index/100 ml. TTC tested positive for coliform bacteria at 44.2°C. All the water samples of the study area exceeded the permissible counts of WHO and that (zero and minimal counts) of the control site (National Geophysical Research Institute) water samples. Excessively high colony numbers indicate that the water is highly contaminated with microorganisms and is hazardous for drinking purposes. Bacteriological pollution of drinking water supplies caused diarrhoeal illness in Bholakpur, which is due to the infiltration of contaminated water (sewage) through cross connection, leakage points, and back siphoning.     

Origin and characterisation of microparticles in an ice core from the Central Dronning Maud Land, East Antarctica

The scanning electron microscopy-energy dispersive spectroscopic (SEM-EDS) study of selected samples from an ice core collected from Central Dronning Maud Land (CDML), East Antarctica, revealed several microparticles. They are mainly siliceous and carbonaceous particles and have distinct variations in their shape and composition. The morphology and major element chemistry of the particles suggest their origin from either volcanic eruptions or continental dust. The EDS analysis revealed that the volcanic particles are enriched in silica (average SiO2 62%), compared to the continental dust particle (average SiO2 56%). We found that the tephra relating to Agung (1963) and Karkatau (1883) volcanic eruptions, as recorded, in the ice core harbored microbial cells (both coocoid and rods). The occurrence of organic and inorganic particles which bear relation to volcanic eruption and continental dust implies significant environmental changes in the recent past.