Optimizing electron spin resonance detection of hydroxyl radical in water

The parameters affecting the electron spin resonance (ESR) detection of hydroxyl free radical in water are studied and optimized. The hydroxyl radical is generated by the Fenton reaction with iron (II) ammonium sulfate and hydrogen peroxide reacting in a phosphate buffer using N-tert-butyl-alpha-phenylnitron as the spin trap. The concentrations of Fe²⁺, H₂O₂, and phosphate buffer are the parameters studied. The Taguchi method and the orthogonal experiment design were used to evaluate the effects of these parameters on the ESR signal intensity. By the analysis of the signal-to-noise ratio and the analysis of variance, the order of importance of the various parameters on the hydroxyl radical formation is determined for optimal ESR detection of hydroxyl radical. The results will help the development of water purification technologies using hydroxyl free radical as a green oxidant.     

Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil

A pot experiment was conducted to study the effects of EDTA and low molecular weight organic acids (LMWOA) on the pH, total organic carbon (TOC) and heavy metals in the soil solution in the rhizosphere of Brassica juncea grown in a paddy soil contaminated with Cu, Zn, Pb and Cd. The results show that EDTA and LMWOA have no effect on the soil solution pH. EDTA addition significantly increased the TOC concentrations in the soil solution. The TOC concentrations in treatments with EDTA were significantly higher than those in treatments with LMWOA. Adding 3 mmol kg(-1) EDTA to the soil markedly increased the total concentrations of Cu, Zn, Pb and Cd in the soil solution. Compared to EDTA, LMWOA had a very small effect on the metal concentrations. Total concentrations in the soil solution followed the sequence: EDTA > citric acid (CA) approximately oxalic acid (OA) approximately malic acid (MA) for Cu and Pb; EDTA > MA > CA approximately OA for Zn; and EDTA > MA > CA > OA for Cd. The labile concentrations of Cu, Zn, Pb and Cd showed similar trends to the total concentrations.     

Spatial distribution of heavy metals in urban soils of Naples city (Italy)

Concentrations of surface and sub-surface soil Cu, Cr, Pb and Zn in the Naples city urban area were measured in 1999. Contourmaps were constructed to describe the metals spatial distribution. In the most contaminated soil samples, metals were speciated by means of the European Commission sequential extraction procedure. At twelve sites, Cu, Pb and Zn levels in soil were compared with those from a 1974 sampling. Many surface soils from the urban area as well as from the eastern industrial district contained levels of Cu, Pb and Zn that largely exceeded the limits (120, 100 and 150 mg kg(-l) for Cu, Pb and Zn, respectively) set for soils of public, residential and private areas by the Italian Ministry of Environment. Chromium values were never above regulatory limits(120 mg kg(-1)). Copper apparently accumulates in soils contiguous to railway lines and tramway. Cu and Cr existed in soil mainly inorganic forms (-68%), whereas Pb occurs essentially as residual mineral phases (77%). The considerable presence of Zn in the soluble, exchangeable and carbonate bound fraction (23%) suggests this element has high potential bioavailability and leachability through the soil. Concentrations of Cu, Pb and Zn have greatly increased since the 1974 sampling, with higher accumulation in soils from roadside fields.     

Effects of fenoxycarb exposure on complete larval development of the xanthid crab,Rhithropanopeus harrisii

Pest control agents, such as juvenile hormone analogues (JHA), have been developed to limit effects on non-target organisms that co-inhabit insect pest habitats. Rhithropanopeus harrisii, an estuarine xanthid crab, was used to observe the impacts of the JHA, fenoxycarb, on the pattern of complete larval development as well as survival of larvae and successful metamorphosis to first crab stage. Significant mortality occurred in the first of four zoeal stages (after 2-3 days of exposure) at the highest treatment of 240 microg fenoxycarb/l and in megalopae exposed to 48 microg fenoxycarb/l. The time required to metamorphose to the first crab stage was significantly increased for megalopae in all treatments 48 microg/l. This delay in development was sufficient to significantly prolong the entire developmental period from zoea to crabs. Unexposed larvae developed to crabs in an average of 16 days; larvae exposed to >/=48 microg/l required 19-20 days. Reduced survival and extended duration of developing larval stages in the life history of a benthic invertebrate may alter the population dynamics of these organisms in the estuary.     

Trace elements and microbiological parameters in farmed Nile tilapia with emphasis on muscle,water, sediment and feed

Fish may bioaccumulate contaminants from the aquatic environment and extend them to the food chain provoking risks to human health. This study evaluated the microbiological parameters of the pond´s water and trace elements concentrations in samples of water, sediment, feed and muscle of farmed Nile tilapia used for human consumption in southern Brazil. A total of 240 fish were collected from 12 tilapia farms. Sediment, tank water and dry ration used in the animals' diet were collected for analysis. Analysis were performed by Energy Dispersion X-ray Fluorescence (EDXRF), Inductively Coupled Plasma Mass Spectrometer (ICP-MS), Induced Coupled Plasma Optical Emission Spectrometer (ICP-OES), and Atomic Absorption Spectrometer (AAS-VGA). In addition, the microbiological analysis of the water was carried out. The concentrations of Se, I, Fe, Cu and Zn in fish muscle were higher than the recommended by the Brazilian legislation, considering the advised daily intake for adults. The arsenic element had concentrations above the limit stipulated by the present Brazilian legislation, observed in all samples of muscle, sediment and tank water highlighting a possible environmental and fish contamination by the toxic element. Moreover, the arsenic concentration in the water presented a positive correlation (ρ?=?0.33) with arsenic in the muscle, suggesting that tilapia is a good environmental bioindicator, once they properly reflect the levels of arsenic in the water. It is suggested to perform an arsenic speciation for quantification of the inorganic form and accurate assessment of the degree of toxicity in the muscle samples and risks it can bring to human health. Regarding the other potentially toxic elements (Hg, Pb and Cd), and microbiological analysis of water it was verified that the consumption of the fish in question does not raise risks, since the values are within a quality benchmark established by law. The concentration of total and fecal coliforms in pond´s water in the facilities was in agreement with the microbiological indexes required by the legislation of CONAMA class II. Western region presented the lowest concentrations of fecal coliforms when compared to the other regions. There was no significant difference in the microbiological counts of total heterotrophic bacteria, Vibrio spp. and Pseudomonas spp. among the regions.     

Bone mineral density in male Baltic grey seal (Halichoerus grypus)

Bone mineral density (mg cm(-3)) was studied in male Baltic grey seals (4-23 years of age) by noninvasive computed tomography (pQCT). The material was grouped according to year of collection. Group A: 1850-1955, a period before the main introduction of organochlorines (OCs); Group B: 1965-1985, a period with very high OC contamination; and Group C: 1986-1997, a period with decreasing concentrations of OCs. The reproducibility of the measurements was good with a Coefficient of Variation (CV) ranging from 0.1% to 2.1%. Trabecular bone mineral density of the radius was significantly higher in specimens collected 1986-1997 than in those collected 1965-1985 (p < 0.05). Cortical bone mineral density of the mandible was significantly lower in specimens collected 1986-1997 compared with those collected 1850-1955 (p < 0.05). These results indicate different responses over time in trabecular and cortical bone. During the period of very high OC contamination (1965-1985), trabecular bone density was lowest, whereas cortical bone density was lowest in specimens collected 1985-1997, representing a period of fairly low OC contamination. The mechanisms behind these effects are not known. However, it can be assumed that OCs are involved. Information about residue levels of OCs in the studied individuals is lacking and, therefore, it was not possible to evaluate the impact of OCs in this respect.     

Soil carbon pools and fluxes in urban ecosystems

The transformation of landscapes from non-urban to urban land use has the potential to greatly modify soil carbon (C) pools and fluxes. For urban ecosystems, very little data exists to assess whether urbanization leads to an increase or decrease in soil C pools. We analyzed three data sets to assess the potential for urbanization to affect soil organic C. These included surface (0-10 cm) soil C data from unmanaged forests along an urban-rural gradient, data from "made" soils (1 m depth) from five different cities, and surface (0-15 cm) soil data of several land-use types in the city of Baltimore. Along the urban-rural land-use gradient, we found that soil organic matter concentration in the surface 10 cm varied significantly (P=0.001). In an analysis of variance, the urban forest stands had significantly (P=0.02) higher organic C densities (kg m(-2) to 1 m depth) than the suburban and rural stands. Our analysis of pedon data from five cities showed that the highest soil organic C densities occurred in loamy fill (28.5 kg m(-2)) with the lowest occurring in clean fill and old dredge materials (1.4 and 6.9 kg m(-2), respectively). Soil organic C densities for residential areas (15.5 +/- 1.2 kg m(-2)) were consistent across cities. A comparison of land-use types showed that low density residential and institutional land-uses had 44 and 38% higher organic C densities than the commercial land-use type, respectively. Our analysis shows that as adjacent land-use becomes more urbanized, forest soil C pools can be affected even in stands not directly disturbed by urban land development. Data from several "made" soils suggests that physical disturbances and inputs of various materials by humans can greatly alter the amount C stored in these soils.     

Effects of clearfelling on stream and soil water aluminium chemistry in three UK forests

Data are presented demonstrating how clearfelling has changed soil and stream water aluminium chemistry. For soil waters, a strong empirical relationship was observed between inorganic aluminium (Al(inorg)) and total inorganic anion (TIA) concentrations. Before felling, chloride and sulphate accounted for the largest proportion of the TIA concentration. After felling, in soils where nitrification was active, nitrate became increasingly important. Where this led to an increase in TIA, Al(inorg) concentrations increased. Over five years, nitrate concentrations have fallen, along with TIA, resulting in a sympathetic decline in Al(inorg). Streams draining clearfelled areas initially became more acid, although chloride and sulphate concentrations decreased. Stream water nitrate concentrations increased soon after felling and remained higher than controls for up to four years. While nitrate concentrations were high, Al(inorg) remained unchanged. Subsequently, as nitrate and TIA decreased, Al(inorg) also declined to concentrations below those in the control stream. Clearfelling upland forests will not necessarily result in immediate improvements in water quality, although long-term benefits may be seen before canopy-closure of the next crop.     

Comparison of episodic acidification in Canada, Europe and the United States

Episodic acidification is practically a ubiquitous process in streams and drainage lakes in Canada, Europe and the United States. Depressions of pH are often smaller in systems with low pre-episode pH levels. Studies on European surface waters have reported episodes most frequently with minimum pH levels below 4.5. In Canada and the United States, studies have also reported a number of systems that have had minimum pH levels below 4.5. In all areas, change in water flowpath during hydrological events is a major determinant of episode characteristics. Episodic acidification is also controlled by a combination of other natural and anthropogenic factors. Base cation decreases are an important contributor to episodes in circumneutral streams and lakes. Sulphate pulses are generally important contributors to episodic acidification in Europe and Canada. Nitrate pulses are generally more important to episodic acidification in the Northeast United States. Increases in organic acids contribute to episodes in some streams in all areas. The sea-salt effect is important in near-coastal streams and lakes. In Canada, Europe and the United States, acidic deposition has increased the severity (minimum pH reached) of episodes in some streams and lakes.     

Contribution of canopy leaching to sulphate deposition in a Scots pine forest

Radioactive sulphate (35SO4) was applied to the soil below a Scots pine forest on 23 June 1989, and its movement into the canopy and into throughfall and stemflow was measured over 4 months. The specific activity, Bq (mg S)(-1), of the canopy increased monotonically; uptake by current-year (1989) expanding needles was initially twice as fast as by older needles or live twigs. By 10 October the canopy average specific activity was 62 Bq (mg S)(-1). The specific activity of net throughfall (throughfall + stemflow - rain), deduced from measurements from six throughfall collectors, six stemflow collectors and two rain collectors, fell rapidly from 12.6 Bq (mg S)(-1) in late July to <1 Bq (mg S)(-1) in mid-August. The results suggest (assuming rapid equilibration of 35S with sulphate in soil) that root-derived sulphate contributed c. 3% of sulphate in net throughfall and that dry deposition of SO2 and sulphate particles contributed c. 97% of the 0.56 g S m(-2) measured in net throughfall over the period. Simultaneous measurements of SO2 at canopy height and of NH3 above and within the canopy gave mean concentrations of 5.9 and 0.86 microg m(-3), respectively, sufficient to account for the sulphate measured in net throughfall only if codeposition of NH3 and SO2 occurred to canopy surfaces. The large values of specific activity observed in July, however, indicate that throughfall composition may be closely related to recent soil input of sulphate, and that equilibrium cannot be safely assumed. The possibility of a significant contribution of soil-derived sulphate to sulphate deposition in net throughfall cannot be ruled out on the basis of this experiment.