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.     

The Influence of Linear Elements on Plant Species Diversity of Mediterranean Rural Landscapes: Assessment of Different Indices and Statistical Approaches

This paper mainly aims to study the linear element influence on the estimation of vascular plant species diversity in five Mediterranean landscapes modeled as land cover patch mosaics. These landscapes have several core habitats and a different set of linear elements -habitat edges or ecotones, roads or railways, rivers, streams and hedgerows on farm land- whose plant composition were examined. Secondly, it aims to check plant diversity estimation in Mediterranean landscapes using parametric and non-parametric procedures, with two indices: Species richness and Shannon index.Land cover types and landscape linear elements were identified from aerial photographs. Their spatial information was processed using GIS techniques. Field plots were selected using a stratified sampling design according to relieve and tree density of each habitat type. A 50×20 m² multi-scale sampling plot was designed for the core habitats and across the main landscape linear elements. Richness and diversity of plant species were estimated by comparing the observed field data to ICE (Incidence-based Coverage Estimator) and ACE (Abundance-based Coverage Estimator) non-parametric estimators.The species density, percentage of unique species, and alpha diversity per plot were significantly higher (p < 0.05) in linear elements than in core habitats. ICE estimate of number of species was 32% higher than of ACE estimate, which did not differ significantly from the observed values. Accumulated species richness in core habitats together with linear elements, were significantly higher than those recorded only in the core habitats in all the landscapes. Conversely, Shannon diversity index did not show significant differences.     

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).     

Lichen and moss bags as monitoring devices in urban areas. Part II: trace element content in living and dead biomonitors and comparison with synthetic materials

Lobes of the lichen Pseudevernia furfuracea (L.) Zopf and shoots of the moss Hypnum cupressiforme Hedw. were subjected to different treatments (water washing, oven drying, HNO3 washing, NH4-oxalate extraction) to assess the influence of vitality on accumulation efficiency, during a 6-week exposure in bags in two Italian cities, Trieste and Naples. No trend emerged between treatments, in terms of accumulation ability, for major and trace elements. Only water-washed lichens showed an increased C and N content after exposure in both cities. Element concentrations generally reached higher values in mosses than in lichens, especially for Al, Fe, and Zn (both cities), and for Cu, Mg and Na (Naples). Surface development strongly influenced accumulation capacity of the biomonitors. Quartzose and cation exchange filters revealed, on a weight basis, a poor performance. In urban environments, surface interception of atmospheric particulate seems to play a major role in accumulation, irrespective of organism vitality.     

GCM-based analysis of water availability along the Tone River and Tokyo Metropolitan Area under climatic changes

Tone River supplies most of the water requirements of the Tokyo Metropolitan Area (TMA). Lowering of Tone flow and yearly fluctuation, however, is causing water shortage along TMA nowadays. This study investigated the future water availability scenarios under climatic changes. A state-of-the-art approach to utilize the output of several GCM has been demonstrated to investigate the future water availability scenarios for TMA from the Tone River. An integrated modeling approach for water balance considering several hydrological risk indices was adopted to quantify the future changes in this case. It is observed that the future summer precipitation along the Tone basin is going to be increased considerably, while an almost constant or decreasing trend is observed for winter season. Natural flow availability for winter or spring seasons thus can be crucial under future scenarios. After reservoir routing, the hydrological risk indices estimated, however, were not found to be changed significantly due to the presence of a robust reservoir system at the upstream.     

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.