Heterogeneous photocatalytic degradation of prometryn in aqueous solutions under UV-Vis irradiation

In this study, the heterogeneous photocatalytic degradation of prometryn using TiO(2) as photocatalyst was investigated. The main objectives of the study were: (I) to evaluate the kinetics of the pesticide disappearance, (II) to compare the photocatalytic efficiency of two different types of TiO(2), (III) to examine the influence of various parameters such as initial concentration of pesticide or catalyst and presence of oxidants (H(2)O(2) and K(2)S(2)O(8)), (IV) to evaluate the degree of mineralization and (V) to assess the detoxification efficiency of the studied processes. The experiments were carried out in a 500 ml pyrex UV reactor equipped with a 125 W high-pressure mercury lamp surrounded by a pyrex filter blocking wavelengths below 290 nm. Prometryn concentration was determined using HPLC. It was found that the degradation of the pesticide follows the first order kinetics according to the Langmuir-Hinshelwood model. Parameters like the type and concentration of the catalyst affect the degradation rate. A synergistic effect was observed when an oxidant was added in the TiO(2) suspensions increasing the reaction rate of photodegradation. In order to examine the extent of pesticide mineralization, DOC measurements were carried out. After 6h of illumination, mineralization was achieved up to almost 70%. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fisheri, in order to compare the acute toxicity of prometryn and its photoproducts. The detoxification efficiency was found to be dependent on the studied system and it did not follow the rate of pesticide disappearance.     

Risk assessment of trace elements in the stomach contents of Indo-Pacific Humpback Dolphins and Finless Porpoises in Hong Kong waters

The potential health risks due to inorganic substances, mainly metals, was evaluated for the two resident marine mammals in Hong Kong, the Indo-Pacific Humpback Dolphin (Sousa chinensis) and the Finless Porpoise (Neophocaena phocaenoides). The stomachs from the carcasses of twelve stranded dolphins and fifteen stranded porpoises were collected and the contents examined. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V and Zn) were determined by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of risks of adverse effects was undertaken using two toxicity guideline values, namely the Reference Dose (RfD), commonly used in human health risk assessment, and the Toxicity Reference Value (TRV), based on terrestrial mammal data. The levels of trace metals in stomach contents of dolphins and porpoises were found to be similar. Risk quotients (RQ) calculated for the trace elements showed that risks to the dolphins and porpoises were generally low and within safe limits using the values based on the TRV, which are less conservative than those based on the RfD values. Using the RfD-based values the risks associated with arsenic, cadmium, chromium, copper, nickel and mercury were comparatively higher. The highest RQ was associated with arsenic, however, most of the arsenic in marine organisms should be in the non-toxic organic form, and thus the calculated risk is likely to be overestimated.     

Characterization and Identification of the Sources of Chromium, Zinc, Lead, Cadmium, Nickel, Manganese and Iron in Pm10 Particulates at the Two Sites of Kolkata, India

Monitoring of ambient PM₁₀ (particulate matter which passes through a size selective impactor inlet with a 50% efficiency cut-off at 10 μm aerodynamic diameter) has been done at residential (Kasba) and industrial (Cossipore) sites of an urban region of Kolkata during November 2003 to November 2004. These sites were selected depending on the dominant anthropogenic activities. Metal constituents of atmospheric PM₁₀ deposited on glass fibre filter paper were estimated using Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES). Chromium (Cr), zinc (Zn), lead (Pb), cadmium (Cd), nickel (Ni), manganese (Mn) and iron (Fe) are the seven toxic trace metals quantified from the measured PM₁₀ concentrations. The 24 h average concentrations of Cr, Zn, Pb, Cd, Ni, Mn and Fe from ninety PM₁₀ particulate samples of Kolkata were found to be 6.9, 506.1, 79.1, 3.3, 7.4, 2.4 and 103.6 ng/m³, respectively. The 24 h average PM₁₀ concentration exceeded national ambient air quality standard (NAAQS) as specified by central pollution control board, India at both residential (Kasba) and industrial (Cossipore) areas with mean concentration of 140.1 and 196.6 μg/m³, respectively. A simultaneous meteorology study was performed to assess the influence of air masses by wind speed, wind direction, rainfall, relative humidity and temperature. The measured toxic trace metals generally showed inverse relationship with wind speed, relative humidity and temperature. Factor analysis, a receptor modeling technique has been used for identification of the possible sources contributing to the PM₁₀. Varimax rotated factor analysis identified four possible sources of measured trace metals comprising solid waste dumping, vehicular traffic with the influence of road dust, road dust and soil dust at residential site (Kasba), while vehicular traffic with the influence of soil dust, road dust, galvanizing and electroplating industry, and tanning industry at industrial site (Cossipore).     

Modified Fenton reaction for trichlorophenol dechlorination by enzymatically generated H2O2 and gluconic acid chelate

Glucose oxidase is a well-known enzyme that catalyzes the oxidation of β-d-glucose to produce gluconic acid and hydrogen peroxide. Fenton reaction is a powerful oxidation technology used for the oxidation of groundwater pollutants. For the application of Fenton reaction in groundwater remediation, successful operation of Fenton reaction near neutral pH, and on-site generation of both H₂O₂ and chelate will be beneficial. The focus of this experimental study was to couple the glucose oxidation reaction with chelate-based Fenton reaction. The idea was to use the hydrogen peroxide and chelate gluconic acid generated during glucose oxidation for the dechlorination of 2,4,6-trichlorophenol (TCP) by Fenton reaction. The oxidation of glucose was achieved using the enzyme in free and immobilized forms. The rate of production of hydrogen peroxide was determined for each system, and was used to estimate the time required for complete consumption of glucose during the process, thus avoiding any traces of glucose in the Fenton reaction. In the case of free enzyme reaction, separation of the enzyme was achieved using an ultrafiltration membrane before initiating the Fenton reaction. The oxidation of TCP by Fenton reaction was performed at varying ratios of gluconic acid/Fe, and its effect on the decomposition of TCP and H₂O₂ was studied. TCP degradation was studied both in terms of parent compound degradation and free chloride generation.     

Occurrence and fate of pesticides in four contrasting agricultural settings in the United States

Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.     

Municipal waste compost as an alternative to cattle manure for supplying potassium to lowland rice

The importance of the use of potassium in agriculture is increasing in South Asia for making most productive use of the nutrient in terms of economic returns. Nutrient supply traditionally by cattle manure is constrained by its insufficient availability. Municipal waste compost may be an alternative source of nutrient supplements. Field experiments were conducted at the Experimental Farm of Calcutta University, West Bengal, India during the wet seasons of 1997, 1998 and 1999 on flooded lowland rice. Potassium fractions in municipal waste compost and cattle manure were determined by sequential extraction and also the potassium uptake by rice to compare the effectiveness of municipal waste compost with traditional manure. Potassium was significantly bound to the organic matter in municipal waste compost. Potassium uptake by rice grain and straw increased significantly with the combined application of organics and fertilizers and it was higher in grain than in straw. Water-soluble and non-exchangeable potassium contents of municipal waste compost and cattle manure were highly correlated with the uptake of potassium by straw and grain. Exchangeable and residual potassium were also significantly correlated with the uptake of potassium by straw and grain of rice. Much higher uptake of K in rice straw and rain resulted from applying the manures in conjunction with fertilizers than when applied singly.     

Geochemical characteristics of surficial sediments in a tropical estuary, south-west India

Geochemical characteristics of surficial sediments in the Panangad region of Cochin estuary, the largest brackish-water humid ecosystem in the south-west coast of India, were analysed. Temporal variations in nutrient stoichiometry, seasonal characteristics of redox elements Fe and S, and the phosphorus geochemistry were employed for the purpose. The stoichiometric analysis pointed towards autochthonous origin of organic matter, possibility of nitrogen limitation, and allochthonous modification of redox conditions. Seasonal variations were not statistically significant for all the geochemical parameters, whereas significant spatial variations were observed with lower values at sandy stations, suggesting that the texture of the sediments is the main factor influencing the sediment geochemistry. Significant inter-relations between the geochemical parameters also suggest a common control mechanism. Based on these geochemical characteristics, the study region can be effectively categorized into two distinct zones, viz. (1) erosion and transportation and (2) deposition zones.     

Application of GIS in the study of mass transport of pollutants by Adyar and Cooum Rivers in Chennai, Tamilnadu

Residential, industrial, commercial, institutional and recreational activities discharge degradable and non-degradable wastes that reach the coastal water through rivers and cause coastal pollution. In the present study, mass transport of pollutants by Adyar and Cooum Rivers to the coastal water as a result of land-based discharges was estimated during low tide. The lowest and the highest flow recorded in Adyar varied from 514.59 to 2,585.08×10⁶ litres/day. Similarly, the flow in Cooum River fluctuated between 266.45 and 709.34×10⁶ litres/day. The present study revealed that the Adyar River transported 53.89–454.11 t/d of suspended solids, 0.06–19.64 t/d of ammonia, 15.95–123.24 t/d of nitrate and 0.4–17.86 t/d of phosphate, 0.004–0.09 kg/d of cadmium, 0.15–1.29 kg/d of lead and 3.03–17.58 kg/d of zinc to the coastal water owing to its high discharge. Similarly, the Cooum River transported 11.87–120.06 t/d of suspended solids, 0.08–58.7 t/d of ammonia, 6.11–29.25 t/d of nitrate and 0.66–10.73 t/d of phosphate, 0.003–0.021 kg/d of cadmium, 0.02–0.44 kg/d of lead and 1.36–3.87 kg/d of zinc. A higher concentration of suspended solids was noticed in post monsoon and summer months. An increase in the mass transport of ammonia, nitrate, phosphate in summer months (April and May) and an increase in the mass transport of cadmium, lead and zinc were observed in monsoon months (October–December) in both the rivers. Thus mass transport of pollutants study reveal that Cooum and Adyar Rivers in Chennai contribute to coastal pollution by transporting inorganic and trace metals significantly through land drainage.