Modelling the contribution of different sources of sulphur to atmospheric deposition in the United Kingdom

In order to understand relationships between sources and receptors of atmospheric deposition, computer models must be used. This paper describes a Lagrangian acid deposition model that represents emissions of trace species across Northern Europe. The chemistry of sulphur dioxide, dimethyl sulphide and hydrogen sulphide is represented and the model tested against estimates of UK wet and dry deposition. Mean UK wet and dry deposition for the period 1992–1994 was 206 and 145 ktonne S yr^-1, respectively. The model predicted wet and dry deposition of 222 and 166 ktonne S yr^-1, in good agreement with measurements. The model has been used to examine the sources of deposited S to the UK. For a base year of 1992, 86% of the UK's SO₂ emissions are exported. The S deposition attributable from mainland European sources was 36% of the UK total S deposition, in good agreement with other UK models but this differs substantially from the calculations of the EMEP model. Natural sources of S deposition from planktonic emissions of dimethyl sulphide, biological emissions of hydrogen sulphide and non-eruptive volcanic emissions of sulphur dioxide contributed approximately 1% of the modelled UK S deposition, of which 95% originated from dimethyl sulphide. The explicit chemical scheme for dimethyl sulphide incorporated into the model showed that 24% of the resultant deposited S was methane sulphonic acid. Boundary conditions of the model were tested and it was found that initialisation of sulphur dioxide and sulphate concentrations to representative ambient conditions had a very small effect. The modelled contribution of UK and European sources to UK S deposition was approximately 40 and 60%, respectively, showing the dramatic change arising from projected UK SO₂ emissions in 2010. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chlorobiphenyl contaminants at Pladda and Garroch Head in the Firth of Clyde in relation to sewage sludge input

Sewage sludge dumped at Garroch Head in the Firth of Clyde contains significant quantities of chlorinated hydrocarbons, such as polychlorinated biphenyls (CBs). These compounds are lipophilic and resistant to degradation. They accumulate in the biota either from the water column or through the food chain, particularly in tissue with a high lipid content. Bottom dwelling fish, such as plaice, in the vicinity of the dump site will accumulate CBs from their environment. Eighteen of the 209 CBs were measured in plaice livers from the Garroch Head dump site and from Pladda, a site reasonably remote from the dump site but also in the Clyde, over a 7 year period prior to the cessation of dumping in December 1998. Concentrations of the congeners in the liver of fish caught at the dump site were, in general, higher than those in the liver of fish caught at Pladda. Concentrations in the plaice livers for the sum of 18 CBs ranged from 1611 to 8471 micrograms kg-1 lipid for Garroch Head samples and from 336.9 to 2635 micrograms kg-1 lipid for samples from Pladda. The data were evaluated using principal component analysis (PCA). Pattern analysis was undertaken by normalising to the recalcitrant CB 153. Livers from the dump site were found to have a higher proportion of the lower chlorinated CBs. CB patterns were similar at the Garroch Head dump site from year to year, but multivariate techniques showed that there were differences in pattern when normalised to CB 153.     

Adsorption characteristics of a phenoxy acetic acid herbicide on activated carbon

The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) by two powdered coal activated carbons was studied in aqueous solution. The modelling of the adsorption equilibrium showed that the adsorption of 2,4-D fitted a Langmuir isotherm. Adsorption was influenced by the activated carbon type, adsorbent concentration and solution characteristics. The adsorption was found to decrease with an increase in pH over the range 1.5-9. Maximum adsorption occurred at pH approximately 2.5, which corresponds to the 2,4-D pKa value. The amount of 2,4-D adsorbed was also found to depend on the NaCl concentration.     

Ascorbic acid reduction of residual active chlorine in potable water prior to halocarboxylate determination

In studies on the formation of disinfection byproducts (DBPs), it is necessary to scavenge residual active (oxidizing) chlorine in order to fix the chlorination byproducts (such as haloethanoates) at a point in time. Such research projects often have distinct needs from requirements for regulatory compliance monitoring. Thus, methods designed for compliance monitoring are not always directly applicable, but must be adapted. This research describes an adaptation of EPA Method 552 in which ascorbic acid treatment is shown to be a satisfactory means for reducing residual oxidizing chlorine, i.e., HOCl, ClO-, and Cl2, prior to determining concentrations of halocarboxylates. Ascorbic acid rapidly reduces oxidizing chlorine compounds, and it has the advantage of producing inorganic halides and dehydroascorbic acid as opposed to halogenated organic molecules as byproducts. In deionized water and a sample of chlorinated tap water, systematic biases relative to strict adherence to Method 552 were precise and could be corrected for using similarly treated standards and analyte-fortified (spiked) samples. This was demonstrated for the quantitation of chloroethanoate, bromoethanoate, 2,2-dichloropropanoate (dalapon), trichloroethanoate, bromochloroethanoate, and bromodichlorocthanoate when extracted, as the acids, into tert-butyl methyl ether (MTBE) and esterified with diazomethane prior to gas chromatography with electron capture detection (GC-ECD). Recoveries for chloroethanoate, bromoethanoate, dalapon, dichloroethanoate, trichloroethanoate, bromochloroethanoate, bromodichloroethanoate, dibromoethanoate, and 2-bromopropanoate at concentrations near the lower limit of detection were acceptable. Ascorbic acid reduction appears to be the best option presently available when there is a need to quench residual oxidants fast in a DBP formation study without generating other halospecies but must be implemented cautiously to ensure no untoward interactions in the matrix.     

Robust graphical methods for diagnosing trend in irregularly spaced water quality time series

Graphical methods can play an important role in the reliable assessment of trends in typically ill behaved river quality data series both as diagnostic tools and as visual corroborative evidence when assumptions required for formal statistical tests are not met. Robust, graphically-oriented trend diagnosis procedures are presented for data series characterized by nonnormal populations, uneven time spacing, nonmonotonic trend and other factors which can create serious problems for standard parametric time series methods. Cleveland's robust locally weighted regression (RLWR) developed for investigating nonlinearity in x-y scatterplots is adapted as a robust/resistant smoothing filter for the analysis of irregular time series comprising quantitative observations. Low powered RLWR trend lines reveal temporally local phenomena, e.g. abrupt jumps (often associated with point source impacts) and periodicities, while higher powered RLWR yields smooth lines characterizing medium and longer term trends. Simple variants of Tukey smoothing concepts are developed for series with censored observations. Applications to Ontario river quality series reveal that graphical evidence is frequently sufficient to obviate the need for formal trend testing. The methods are generally applicable to most time series.     

A proposed MISA approach to setting limits and assessing compliance

Ontario's MISA program is intended to reduce all municipal and industrial waste loadings and to virtually eliminate the release of persistent toxic contaminants to surface waters. Based on 12-months of effluent monitoring data, effluent limit guidelines will be issued for 9 industrial and municipal sectors. The effluent limits will be based on the best available technology economically achievable and will involve extensive statistical analyses of the monitoring data. Proposed statistical methods for the derivation of effluent limits and assessing compliance are presented, along with brief information on the criteria for selection of pollutants and sample size requirements for the MISA effluent monitoring program. The proposed methods are not the policies of the Ministry of the Environment and may or may not be used for the development of effluent limits.     

Temporal variation in a coral reef community at Pattaya Bay,Gulf of Thailand

Changes in the fringing coral reef community of a small island (Ko Nok) at Pattaya Bay, Gulf of Thailand, were examined at the beginning and at the end of a 3-year period using 7m×7m permanent quadrats for benthic organisms, and visual census along 100m transects for fish. The coral community was dominated by Porites lutea in terms of colony number and areal cover throughout the period. Variations in the community structure parameters on opposite sides of the island indicated increasing dissimilarity with time. Little variation in live coral cover was noted, but colony number and species diversity declined on both sides. The abundance of edible fish species dropped while that of non-edible species increased over the 3-year period, indicating selective removal of the former category through fishing. Impacts from both human and natural influences are implicated in these changes.     

Analysis of two-way layout of count data with negative binomial variation

A number of methods has been proposed for dealing with single-factor or factorial experiments when the requirements for performing the normal theory analysis of variance procedure are not satisfied. This paper suggests the use of the likelihood ratio statistic for testing the main effects and the interaction between the factors in two-way layout of count data following negative binomial distributions with a common dispersion parameter. The likelihood ratio statistic for testing the equality of the dispersion parameters of several groups of count data is also derived. The methods is illustrated by an example concerning the study of spatial and temporal variation of bacterial counts.     

A Method for Ensemble Wildland Fire Simulation

An ensemble simulation system that accounts for uncertainty in long-range weather conditions and two-dimensional wildland fire spread is described. Fuel moisture is expressed based on the energy release component, a US fire danger rating index, and its variation throughout the fire season is modeled using time series analysis of historical weather data. This analysis is used to characterize the seasonal trend in ERC, autocorrelation of residuals, and daily standard deviation and stochastically generate artificial time series of afternoon fuel moisture. Daily wind speed and direction are sampled stochastically from joint probabilities of historical wind speed and direction for the date range of the fire simulation period. Hundreds or thousands of fire growth simulations are then performed using the synthetic fire weather sequences. The performance of these methods is evaluated in terms of the number of ensemble member simulations, one- versus two-dimensional fire spread simulations, and comparison with results from 91 fires occurring from 2007 to 2009. Simulations were found to be in consistent agreement with observations, but trends indicate that the ensemble average of simulated fire sizes were consistently larger than actual fires whereas the farthest extent burned by fires was underestimated.     

Relationship between CH₄ and N₂O flux from soil and their ambient mixing ratio in a riparian rice-based agroecosystem of tropical region

Temporal variations of the ambient mixing ratio of greenhouse gas (CH(4) and N(2)O) in a riparian rice-based agro-ecosystem of tropical region were studied during 2005-2006 in coastal Odisha. The endeavour was made with the hypothesis that the ambient mixing ratio of CH(4) and N(2)O depends on the changes in the flux of CH(4) and N(2)O from the rice fields in the riparian rice ecosystems. A higher ambient mixing ratio of CH(4) was recorded during the tillering to grain filling stages of the rice crop, during both dry and wet seasons. The higher ambient mixing ratio of CH(4) during the wet season may attribute to the higher CH(4) emission from the rice field. The average mixing ratio of CH(4) was recorded as 1.84 ± 0.05 ppmv and 1.85 ± 0.06 ppmv during 2005 and 2006, respectively. The ambient CH(4) mixing ratio was recorded negatively correlated with the average ambient temperature. The N(2)O mixing ratio ranged from 261.57 to 399.44 ppbv with an average of 330.57 ppbv during 2005. However, the average mixing ratio of N(2)O was recorded as 318.83 ± 20.00 ppbv during 2006. The N(2)O mixing ratio was recorded to be negatively correlated with rainfall and average ambient temperature. Significant negative correlation (r = -0.209) of N(2)O with sunshine hours may attribute to the photochemical break down of N(2)O. The temporal variation of N(2)O flux from the rice field does not affect the ambient mixing ratio of N(2)O in the same way as in the case of the ambient mixing ratio of CH(4). However, the higher mixing ratio of N(2)O during the fallow period of the post monsoon period may attribute to the N(2)O flux from soil. Results indicate that intensively cultivated coastal ecosystems can be a major source of ambient greenhouse gas.