Kinetic degradation processes of butyl- and phenyltins in soils

The degradation of organotin compounds (OTC) in agricultural and forest soils is studied in sandy soil samples. Individual experiments involving the three butyl- and the three phenyltins were carried out during 90 d in controlled conditions (darkness, 28 degrees C, aerobic conditions, 13% moisture) and with spiking concentration representative of environmental levels (20-50 micrg(Sn) kg(-1)). After the validation of first-order degradation kinetic model, mechanisms involved throughout the study were considered. Degradation pathways are proposed for butyl- and phenyltins and discussed according to literature data. The degradation of mono- (MBT, MPhT), di-organotins (DBT, DPhT) and TBT is clearly identified as a single successive loss of an organic group whereas TPhT is directly degraded to MPhT. The half-life times were dependent on their substitution degree, ranging from 24 (TPhT) to 220 (MBT) d. The less substituted the OTC is, the more persistent it is. In the range 4.3-5.7, pH does not seem to influence OTC degradation under the present operating conditions. Finally this study shows the significant persistence in soil samples in our experimental conditions for most of studied organotins and highlights the potential impact on soil quality.     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

A GIS-based system for allocating municipal solid waste incinerator compensatory fund

To ease the NIMBY (not in my back yard) syndrome of constructing municipal solid waste (MSW) incinerators in Taiwan, compensatory funding is widely allocated to the impacted communities to gain the acceptance and support of residents living the impacted areas. This paper presents a spatial methodology for distributing a compensatory fund more logically based on the environmental impact on each neighborhood in Taipei City. This method integrates ten impact factors, which have been proposed by a local committee, to evaluate all neighborhoods using mathematical models combined with spatial analyses in an analytic hierarchy process. The compensatory fund is distributed according to the resulting final scores. A GIS (geographic information systems)-based system has been developed to assist in assigning the final scores to the neighborhoods impacted. Results on impact factors and fund distributions are combined; they are included in an information system and displayed in spatial scales. For Taipei City, the impact of air quality during the incinerator operating period is the item of greatest concern to the surrounding residents and thus, it receives a relatively higher weight of 0.2894. As a result, high impact scores were assigned to not only those neighborhoods hosting the incinerators, but also the neighborhoods where the maximum particulate air pollutants occurred. This approach could be applicable to other MSW incinerators with similar environmental impact problems and interest in compensation schemes.     

Copper extraction effectiveness and soil dissolution issues of EDTA-flushing of artificially contaminated soils

Ethylenediaminetetraacetic acid (EDTA) was used as a reference chelating agent in column experiments to investigate the effectiveness of chelant-enhanced flushing of soils artificially contaminated under various conditions (low/high Cu loading, and aging). The associated soil dissolution issues were of particular concern. Dissolution of indigenous Fe/Al oxides, Ca carbonates and organic matter was monitored over the course of flushing. Regardless of contamination condition, above 85% extraction efficiency could be accomplished by 10(-2) and 10(-3)M EDTA-flushing, but not 10(-4)M. The Cu extraction kinetics positively correlated to EDTA concentration but inversely to Cu loading in soils. In addition to extraction from weakly sorbed fractions, a large portion of Cu was extracted from oxide, organic matter and residual fractions, which appears to derive from soil dissolution. Cumulative dissolved amounts of Fe, Al, and Ca were found to reach as high as hundreds of mgkg(-1), which were comparable to Cu contamination. Soil organic matter, which is known to strongly interact with Fe and Al oxides, was also mobilized. The rate and extent of these soil dissolutions were also positively correlated to EDTA concentration. Therefore, the co-extraction of soil minerals and organic matter during chelant-enhanced flushing, which would alter both physical structure and chemical properties of the soils, is detrimental to future land use and deserves greater attention. The concentration of chelating agent is the most crucial factor for an effective soil flushing with minimal damage.     

Leak detection of hydrogen–natural gas mixtures in pipes using the characteristics method of specified time intervals

This paper presents a technique for detection and location of leaks in a single pipe, by means of transient analysis, of hydrogen–natural gas mixtures flows. The method uses transient pressure waves initiated by the sudden closure of a downstream shut-off valve. The presence of a leak in a pipe partially reflects these pressure waves and allows for the location of the leak. Pressure waves are governed by two coupled non-linear, hyperbolic partial differential equations with pressure dependent coefficients. The fluid pressure and velocity are considered as two principal dependent variables. To determine the leak location, the mathematical formulation has been solved by the characteristics method of specified time intervals. The computed results describe the influence of the leak on pressure time-history and the effect of hydrogen mass fraction in the mixture on the leak discharge behaviour. It was found that transient pressure is much important in the case of hydrogen than that in the case of natural gas.     

Supply-side ecology of the brown mussel,<Emphasis Type="Italic"> Perna perna</Emphasis>: an investigation of spatial and temporal variation in,and coupling between,gamete release and larval supply

Sampling of recruitment-associated variables of Perna perna was done approximately monthly for 14 months at intertidal locations 500 m apart, nested within sites 25 km apart. Paired with intertidal locations were nearshore locations, 600 m to sea. Sampling assessed spawning, densities of larvae in the water column and densities of late plantigrades and juveniles on the shore. Major events in each variable were synchronous over larger scales (10s of kilometres) while subsidiary events were synchronised at smaller scales, varying within sites (100s of metres) or even within locations (metres). This suggests that the processes driving major events operated over large scales while processes operating at much more local scales drove less intense, more localised events. A major spawning event occurred at all locations in May–June 1998. Weaker spawning events occurred at different times in different locations. Larvae were found on 80% of sampling occasions, densities peaking in January–March 1998 and 1999 at all locations. Plantigrades and juveniles showed less clear patterns, with considerable residual variation. There was no sign of strong coupling among variables with few significant direct or cross correlations. The major sources of variability shifted from time to space as one progressed from spawning, to plantigrade density to juvenile density. For spawning, time was the most important source (58%) of heterogeneity and space accounted for little (8%) of the total variance. For larvae and late plantigrades, time was still the most important source of variability (41% and 33%, respectively), but space was a much more substantial component. For juveniles, small-scale (residual) spatial variability dominated total variability (75%). This strongly suggests the importance of hydrography and its effects on variation in delivery of larvae to the intertidal from offshore. These findings also indicate greater spatial heterogeneity as recruits age, reflecting small-scale variations in larval delivery and the increasing importance of post-settlement mortality.Communicated by G.F. Humphrey, Sydney     

The nonlinearity and related band strength of carbon monoxide when applied in ambient air measurement using open long-path Fourier transform infrared spectrometry

The accuracy of CO concentration determination by open-path Fourier transform infrared (FTIR) spectrometry has been re-evaluated in detail. The evaluation focuses on the correction of the calibration curve--the integrated intensity of a standard spectrum--that is used as a comparison spectrum when doing quantitative analysis of CO. Results show that the calibration curve (with 0.5 cm(-1) or 1 cm(-1) resolution) is apparently inclined to be nonlinear under standard conditions, and that the threshold point of nonlinearity is approximately 0.1 atm-cm. Two commercial FTIR field monitoring systems have been used to investigate the nonlinearity trend. The experimental method consists of using open-path FTIR systems in combination with nondispersive infrared (NDIR) monitors to establish the calibration curve in a semi-closed corridor The results have been double-checked using closed-cell dynamic equilibrium systems. When the optical density is larger than a certain value, the curves begin to bend, and when the optical density approaches zero, the band strength is around 178 +/- 3 atm(-1) cm(-2) and 173 +/- 2 atm(-1) cm(-2), respectively, for 0.5 and 1 cm(-1) resolution at standard temperature and pressure (STP). These values are quite different from other published data that have been acquired by the pressurized method or by high-resolution (<0.006 cm(-1)) spectrometers. It is thought that a higher accuracy is achieved when these new calibration results are used to quantify the CO concentration. The error in concentration determination within 0.1 optical density is less than 2%, and that in the higher optical density region is less than 5%.     

Maternal provisioning for larvae and larval provisioning for juveniles in the toxopneustid sea urchin <Emphasis Type="Italic">Tripneustes gratilla</Emphasis>

Lipid and protein biochemistry of eggs (84 μm in diameter), embryos and early larvae of the tropical echinoid Tripneustes gratilla (Linnaeus 1758) were quantified to determine how maternal provisions are used to fuel development of the echinopluteus. The eggs contained a mean of 30.82 ng lipid and 87.32 ng protein. Energetic lipids were the major lipid component (55.52% of total lipid) with the major class being triglyceride (TG: mean 15.9 ng, 51.58% of total). Structural lipid was dominated by phospholipid (PL: mean 11.18 ng, 36.26% of total). Early embryogenesis was not a major drain on egg energetic lipid and protein. Development of the functional feeding larva used ca. 50% of initial egg energetic lipid and most of this was TG. Maternal TG was still present in the 8-day echinoplutei and it was estimated that this energetic lipid would be depleted in unfed larvae by day 10. There was no change in PL. In a separate experiment lipid biochemistry of rudiment stage larvae and early developing juveniles were quantified to determine how lipids are used during metamorphosis. Fed larvae accumulated lipid (mean 275.49 ng) with TG and PL being the major energetic and structural lipids, respectively. Larval lipid stores were not appreciably depleted by metamorphosis and so were available for the early benthic stage juvenile. Juveniles started their benthic existence with 314 ng total lipid (TG: mean 46.84 ng, 14.9% of total, PL: mean 137.51 ng, 43.67% of total). Nile Red histochemistry and histology showed that the stomach serves as a nutrient storage organ and, that lipid stores accrued by larvae sustain developing juveniles for up to 4 days post settlement. Triglyceride supported both non-feeding stages of development and the prefeeding larval and perimetamorphic benthic stage. In this first study of lipid stores in settlement stage echinoderm larvae, we show that T. gratilla larvae sequester the same major energetic lipid (TG) to support the early juvenile that the female parent provided them to fuel early development.