Studying organic matter molecular assemblage within a whole organic soil by nuclear magnetic resonance

This work shows the applicability of two-dimensional (2D) (1)H-(13)C heteronuclear correlation (HETCOR) nuclear magnetic resonance (NMR) spectroscopy to the characterization of whole soils. A combination of different mixing times and cross polarization (CP) methods, namely Lee-Goldberg (LG)-CP and Ramp-CP are shown to afford, for the first time, intra- and inter- molecular connectivities, allowing for molecular assemblage information to be obtained on a whole soil. Our results show that, for the brackish marsh histosol under study, two isolated domains could be detected. The first domain consists of O-alkyl and aromatic moieties (lignocellulose material), while the second domain is comprised of alkyl type moieties (cuticular material). The role of these domains is discussed in terms of hydrophobic organic compound sorption within soil organic matter (SOM), including the possible effects of wetting and drying cycles.     

Assessment and monitoring of nutrient loading in the sediments of tidal creeks receiving shrimp farm effluent in Quang Ninh, Vietnam

Coastal shrimp farming may lead to the contamination of sediments of surrounding estuarine and marine ecosystems as shrimp farm effluent often contains high levels of pollutants including a range of organic compounds (from uneaten feed, shrimp feces, and living and dead organisms) which can accumulate in the sediments of receiving waterways. The assessment and monitoring of sediment quality in tidal creeks receiving shrimp farm effluent can support environmental protection and decision making for sustainable development in coastal areas since sediment quality often shows essential information on long-term aquatic ecosystem health. Within this context, this paper investigates nutrient loadings in the sediments of tidal creeks receiving shrimp farm effluent in Quang Ninh, Vietnam, which now have a high concentration of intensive and semi-intensive shrimp farms. Sediment samples taken from inside creek sections directly receiving effluent from concentrated shrimp farms (IEC), from main creeks adjacent to points of effluent discharge outside concentrated shrimp farms (OEC), and few kilometers away from shrimp farms (ASF) as reference sites were collected and analyzed before and after shrimp crops to investigate spatial and temporal variation. The results showed that there were statistically significant differences in the concentrations of total nitrogen, total phosphorus, and total organic carbon among IEC, OEC, and ASF sites while the seasonal variation being limited over study times. A sediment nutrient index (SNI) computed from coefficient scores of the factor analysis efficiently summarizes sediment nutrient loads, which are high, albeit quite variable, in canals directly receiving effluents from farms but then decline sharply with distance from shrimp farms. The visualization and monitoring of sediment quality data including SNI on maps can strongly support managers to manage eutrophication at concentrated shrimp farming areas, contributing to sustainable development and management at coastal zones.     

Heavy metals in the liver and muscle of <Emphasis Type="Italic">Micropogonias manni</Emphasis> fish from Budi Lake,Araucania Region,Chile: potential risk for humans

The concentrations of cadmium, lead, manganese and zinc were determined in the fish species Micropogonias manni captured in Budi Lake, Araucanía Region (Chile). The measurements were made by atomic absorption spectroscopy, and the analysis considered the sex, weight and size of the species; the representative samples were taken from the liver and muscle tissue. The method was validated using certified reference material (DOLT-1). The ranges of concentrations found in the muscle tissue were: Cd, not determinate (n.d.)–0.26; Pb, n.d.–1.88; Mn, 0.02–12.17 and Zn, 0.48–39.04 mg kg⁻¹ (dry weight). The concentrations in muscle tissue were generally lower than those found in the liver. With respect to the average concentrations recorded for each metal in the edible part of the fish (muscle tissue), it was found that the levels of Cd, Pb, Mn and Zn are within the ranges published by other authors in similar works and below the maximum concentration limits permitted by current legislation (FAO/WHO 2004; EU 2001) and do not constitute a health hazard for consumers of this species. The results were subjected to statistical analysis to evaluate the correlations between the content of the various metals and the sex, weight and size of each sample.     

Accumulation and leaching potential of some pharmaceuticals and potential endocrine disruptors in soils irrigated with wastewater in the Tula Valley, Mexico

The reuse of wastewater for irrigation of agricultural land is a well established practice but introduces many contaminants into the terrestrial environment including pharmaceuticals and personal care products. This study reports the persistence and leaching potential of a group of acidic pharmaceuticals, carbamazepine, and three endocrine disruptors in soils from the Tula Valley in Mexico, one of the largest irrigation districts in the world that uses untreated wastewater. After irrigation of soil columns with fortified wastewater over the equivalent of one crop cycle, between 0% and 7% of the total added amounts of ibuprofen, naproxen, and diclofenac and between 0% and 25% of 4-nonylphenol, triclosan, and bisphenol-A were recovered from the soil profiles. Carbamazepine was more persistent, between 55% and 107% being recovered. Amounts in leachates suggested that movement through the soil was possible for all of the analytes, particularly in profiles of low organic matter and clay content. Analysis of soil samples from the Tula Valley confirmed the general lack of accumulation of the acidic pharmaceuticals (concentrations from below the limit of detection to 0.61 μgkg(-1)) and endocrine disruptors (concentrations from below the limit of detection to 109 μgkg(-1)) despite continual addition through regular irrigation with untreated wastewater; there was little evidence of movement through the soil profiles. In contrast, carbamazepine was present in horizon A of the soil at concentrations equivalent to several years of additions by irrigation (2.6-7.5 μgkg(-1)) and was also present in the deeper horizons. The persistence and mobility of carbamazepine suggested a potential to contaminate groundwater.     

Methods of characterizing the distribution of exhaust emissions from light-duty, gasoline-powered motor vehicles in the U.S. fleet

Mobile sources significantly contribute to ambient concentrations of airborne particulate matter (PM). Source apportionment studies for PM10 (PM < or = 10 microm in aerodynamic diameter) and PM2.5 (PM < or = 2.5 microm in aerodynamic diameter) indicate that mobile sources can be responsible for over half of the ambient PM measured in an urban area. Recent source apportionment studies attempted to differentiate between contributions from gasoline and diesel motor vehicle combustion. Several source apportionment studies conducted in the United States suggested that gasoline combustion from mobile sources contributed more to ambient PM than diesel combustion. However, existing emission inventories for the United States indicated that diesels contribute more than gasoline vehicles to ambient PM concentrations. A comprehensive testing program was initiated in the Kansas City metropolitan area to measure PM emissions in the light-duty, gasoline-powered, on-road mobile source fleet to provide data for PM inventory and emissions modeling. The vehicle recruitment design produced a sample that could represent the regional fleet, and by extension, the national fleet. All vehicles were recruited from a stratified sample on the basis of vehicle class (car, truck) and model-year group. The pool of available vehicles was drawn primarily from a sample of vehicle owners designed to represent the selected demographic and geographic characteristics of the Kansas City population. Emissions testing utilized a portable, light-duty chassis dynamometer with vehicles tested using the LA-92 driving cycle, on-board emissions measurement systems, and remote sensing devices. Particulate mass emissions were the focus of the study, with continuous and integrated samples collected. In addition, sample analyses included criteria gases (carbon monoxide, carbon dioxide, nitric oxide/nitrogen dioxide, hydrocarbons), air toxics (speciated volatile organic compounds), and PM constituents (elemental/organic carbon, metals, semi-volatile organic compounds). Results indicated that PM emissions from the in-use fleet varied by up to 3 orders of magnitude, with emissions generally increasing for older model-year vehicles. The study also identified a strong influence of ambient temperature on vehicle PM mass emissions, with rates increasing with decreasing temperatures.     

Kinetic analysis of the anaerobic digestion of untreated vinasses and vinasses previously treated with Penicillium decumbens

A kinetic study was carried out on the anaerobic digestion of untreated vinasses and vinasses previously fermented with Penicillium decumbens. Two 1-l volume continuous-flow stirred tank reactors (CFSTR) operating at mesophilic temperature (35 degrees C) were used for the study. One reactor was fed with untreated vinasses (COD concentration of 80.5 g/l) and the other with vinasses previously fermented (COD concentration of 23.0 g/l). Both reactors were operated at organic loading rates in the range of 1.5-7.5 g chemical oxygen demand (COD)/l-d. The results obtained were evaluated using the Chen-Hashimoto methane production model to determine the values of the maximum specific growth rate (micromax) and the model kinetic constant (K) of the process for each case studied. The kinetic constants (micromax and K) were affected by the pre-treatment, and the respective values were 9.6 and 6.9 times higher for pretreated vinasses than those of untreated vinasses. This was significant at the 95% confidence level. This behaviour is believed to be due to the lower levels of phenolic compounds present in the pretreated vinasses, as compared to untreated vinasses, resulting in an improved process performance, kinetics and stability. Finally, the experimental values of methane production were reproduced with deviations equal to or less than 4% and 10% for pretreated and untreated vinasses, respectively.     

A study of the natural biodegradation of two-phase olive mill solid waste during its storage in an evaporation pond

A study of the natural biodegradation of two-phase olive mill solid waste (OMSW) during its storage in an evaporation pond was carried out. This system is traditionally used as the final disposal of this waste or constitutes a previous stage before being processed by cogeneration or anaerobic digestion processes. A laboratory-scale pond with a total volume of 520 l was used. The experiment was carried out between December 2002 and August 2003 covering a total period of 269 days. During the experiment, the variations of temperature (outside and inside the pond), the effective volume of the OMSW in the pond, moisture content, total solids (TS), volatile solids (VS), the total chemical oxygen demand (TCOD), total volatile acids (TVA), pH and cumulative methane production as a function of the operation time were evaluated. The experimental results obtained showed that the characteristics of the two-phase OMSW in the pond were dependent on the time of operation and temperature. During the experiment, three periods were clearly observed and differentiated: (a) An initial period with a rapid reduction of moisture content and effective volume, with an increase of TS, VS and TCOD removals, a decrease of pH and an increase of TVA and methane production until day 21. (b) A second period of slow decrease of moisture content and effective volume, due to the decrease of the ambient temperature. This period took place between day 21 and days 120-150 of assay, and it was characterised by a slight change in the OMSW properties. (c) A third period where the characteristics of the waste in the pond changed considerably due to the increase of the temperature outside the pond. The methane gas production also showed an increase due to the increase of methanogenic activity with the increase of temperature. An empirical model to describe the changes of two-phase OMSW characteristics and methane production with the operation time was developed. The proposed model, based on the use of polynomial equations, took into account the influence of the temperature and fit adequately into the experimental results obtained. It was found that the pond could probably be used as preliminary treatment of two-phase OMSW before its anaerobic digestion process, because a maximum conversion of organic matter to TVA was obtained after an operation time of around 200 days.     

P2: Putting environmental issues in a new light

Pollution prevention can help you see environmental problems for what they really are: waste and inefficiency. © 2000 John Wiley & Sons, Inc.     

Regression method of the hydrophobicity ruler approach for determining octanol/water partition coefficients of very hydrophobic compounds

A regression method was developed for the hydrophobicity ruler approach, which is an indirect method for determining the octanol/water partition coefficients of very hydrophobic compounds. Two constants introduced into the mathematical model were obtained by regression of the absorption data sampled before the partition equilibrium. A water miscible organic solvent was used to increase the solubility of the very hydrophobic compounds in the aqueous solution so that the hydrophobicity scale was reduced and the equilibration was accelerated. Polydimethylsiloxane/methanol aqueous solution and a series of 21 polychlorinated biphenyls (PCBs) were used to demonstrate the regression method. The PCB compounds with known experimental logK(o/w) values served as reference compounds, while the PCB compounds without known logK(o/w) values were determined. The distribution coefficients (logK(p/s)), uptake and elimination rate constants were obtained from the two regression constants for each compound (reference or unknown). The correlation of the logK(p/s) values of the reference PCB compounds with their logK(o/w) values was linear (logK(o/w)=2.69logK(p/s)+0.76, R(2)=0.97). The logK(o/w) values were compared with literature values and suggested that some values from the literature far off the calibration line could be inaccurate. The critical experimental factors, the merits of the regression method were discussed.