Concentration and Distribution of Persistent Organic Pollutants (POPs) in Harbour Dredging Sediments: A Pilot Study Using a Statistical Approach for a More Efficient Characterisation and Management

The Italian guidelines concerning the dumping of dredgingmaterials implies chemical, physical and microbiologicalcharacterisation of dumping sediments collected through aspecific sampling strategy.POP's such as PCB's and organochlorine pesticides, areconsidered as priority pollutants in all the InternationalConventions for the protection of the marine environment, inconsequence of their persistence, toxicity and bioaccumulation capacity.In the present article the concentrations and distribution ofPCB's and organochlorine pesticides in dredging sediments ofPiombino harbour (northern Thyrrenian sea) were investigates.The results showed high POP's concentrations in all the studiedareas. The maximum values were: 3.94 mg kg^-1 dry weight for PCB's(IUPAC Nos. 28; 52; 101, 118; 137; 153; 180; 209); 2.04 mg kg^-1 d.w.for HCH's (-, -, - and -hexachlorocyclohexane isomers); 0.28 mg kg^-1 d.w. for DD's (DDT + DDE + DDD).Subsequently, the data related to each pollutant were treatedwith statistical tests, in order to verify how well the samplingstrategy is able to represent the distribution of contaminantsin the dredging area. Finally, management strategies werederived for the studied dredging sediments.     

Chlorinated Hydrocarbons in Livers of American Mink (Mustela vison) and River Otter (Lutra canadensis) from the Columbia and Fraser River Basins, 1990–1992

We investigated chlorinated hydrocarbon contaminants in aquatic mustelid species on the Fraser and Columbia Rivers of northwestern North America. Carcasses of river otter (Lutra canadensis) (N=24) and mink (Mustela vison) (N=34) were obtained from commercial trappers during the winters of 1990–91 and 1991–92. Pooled liver samples were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), including non-ortho congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Most samples contained detectable concentrations of DDE, PCBs, although there was substantial variability in patterns and trends among neighboring samples. Concentrations of DDE were in some mink and several otter samples from the lower Columbia River elevated (to 4700 g/kg wet weight); excluding one mink sample from the Wenatchee area, mean DDE levels generally decreased between 1978–79 and 1990–92. PCBs were present in all samples. PCB concentrations in otter livers collected from the lower Columbia were ten-fold lower than measured a decade previously; nevertheless, a sample taken near Portland had a mean concentration of 1500 g/kg, within a range of concentrations associated with reproductive effects in captive mink. Concentrations of 2,3,7,8-TCDD and TCDF were generally below detection limits, except for one otter collected near a pulp mill at Castlegar, on the upper Columbia, with 11 ng TCDD/kg in liver. Elevated concentrations of higher chlorinated PCDD/Fs, probably resulting from use of chlorophenolic wood preservatives, were found in both species; one otter sample from the lower Columbia had 2200 ng OCDD/kg. International TCDD toxic equivalent levels in mink (31 ng/kg) and otter (93 ng/kg) from the lower Columbia River approached toxicity thresholds for effects on reproduction in ranch mink.     

Reduction and avoidance of lubricant mist demands an integrated assessment approach

A case study to identify major factors for lubricant mist exposure covered 15 metal machining sites. The investigation included milling, turning, drilling and grinding applications. Systematic analysis considered all relevant data concerning the machine tool, the lubricant and the suction plant. The efficiency of the implemented maintenance program at the installed filter systems was checked by concentration measurements immediately before and after service. All performed measurements of lubricant aerosol and vapor loads upstream and downstream of the installed filter systems were carried out according to VDI 2066 and BIA 3110, respectively. The selection criteria for the sites to be investigated, the systematic nature of the data acquisition and the procedure of the analysis are demonstrated in detail by performing comparisons between selected applications using emulsions and those employing straight oil for lubrication. The results of the study identify recirculation of ventilated air as the major source of workplace exposure to airborne lubricant emissions. More than 60% of the demisters investigated emit air at total lubricant loads (aerosols and vapor) above the limit of 20 mg m-3 at any time of operation; which also means immediately after service. A common reason for exceeded aerosol loads in recirculated air is e.g. the fact that the type of filter system applied is often not suitable for the separation problem. Loads of lubricant vapor are usually higher at the processes which use water emulsions as lubricant. In a quarter of the cases the limits were exceeded solely due to high vapor loads even immediately after service. The exposure can be reduced by replacing the lubricant, installation of a vapor separation plant or avoiding air recirculation. Maintenance time of the demisting system and aerosol separation efficiency of state-of-the-art demisting systems can be expanded by implementation of enhanced preliminary filter stages. This study confirms that appropriate service measures lower both aerosol emissions and lubricant vapor concentrations due to the reduction of exposed oil-wetted surfaces. The performed measurements show no significant relationship between loads of airborne lubricants and the type of machining process. Therefore, investigations at a much more detailed level have to be performed. However, the individual assessment of any workplace due to the complex situation remains essential.     

State estimation in wastewater engineering: Application to an anaerobic process

The use of an extended Kalman filter for state estimation in biological wastewater treatment processes is discussed. The application of the technique requires an adequate mechanistic dynamic model and the identification and modelling of the major sources of stochastic disturbances in the process. The filter allows the on-line tracking of process variables which are not directly measurable. The use of an extended Kalman filter is illustrated through a simulated application to a high rate anaerobic wastewater treatment process.     

Laboratory-polluted soils: a methodological approach to establish equilibrium conditions for different metal chemical forms in soils

An approach based on the number of extractions performed over time was applied to study the time necessary to attain equilibrium conditions between the different chemical forms present in two natural soils laboratory-loaded with heavy metals (Cu(II), Pb(II), Zn(II)). The influence of some soil parameters, such as pH value, cation exchange capacity and organic matter content, on the equilibrium time was evidenced both by the different nature of the soils and by the treatment of soils with paper mill sludge. Equilibrium conditions were determined by studying the metal partitioning in the soil on a case by case basis. The behaviour of the three metals was not the same, and the conditions of equilibrium among the different chemical forms were the result of the amount of heavy metals added as well as of the nature of the soil.     

Impact of automobile emissions on the levels of platinum and lead in Accra,Ghana

Examination of car fleet records in Accra demonstrates an increasing proportion of catalytic converter-equipped cars in the relatively old car fleet (average age 13 years) due to their import from developed countries. However, only leaded petrol is sold in Ghana. Lead anti-knocking additives, which are known to affect catalyst activity and promote thermal sintering and mechanical abrasion, may increase Pt emissions. This possible synergism prompted the concomitant determination of Pb and Pt levels in road dust and roadside soils in Ghana. Both metals followed traffic density with higher concentrations in urban areas compared to remote sites. In urban areas, the range for Pb (365 +/- 93 microg g(-1) for dust and 291 +/- 76 microg g(-1) for soil) reflects precatalyst levels in Europe and the US, while the range for Pt (39 +/- 24 ng g(-1) for dust and 15 +/- 5.3 ng g(-1) for soil) is typical for the same countries. The elevated Pt concentrations were unexpected due to recent introduction of catalysts to Ghana compared to the prolonged use of catalysts in Europe and the US.     

Suspended particulates and bioaerosols emitted from an agricultural non-point source

Suspended particulate and bioaerosol levels were measured at three sites downwind of an agricultural non-point source during the wheat harvesting season. Suspended particulates were detected at mean values ranging from 10000 to 2420 micrograms m-3 at distances of from 20 to 60 m downwind of the source, respectively. Airborne viable bacterial counts were recorded at mean values ranging between 10(4) and 10(6) colony forming units (cfu) m-3, whereas, Gram negative (Gram -ve) bacteria varied between 10(3) and 10(5) cfu m-3. Fungi levels were detected at mean values varying between 10(5) and 10(6) cfu m-3. However, streptomycetes were found at lower counts than those recorded for viable bacteria and fungi. Total viable bacteria, Gram -ve bacteria, fungi and streptomycetes associated hay fragments were determined at mean values of 1.5 x 10(6), 1.6 x 10(3), 2.2 x 10(4) and 6 x 10(3) cfu g-1 of hay, respectively. Cladosporium, white and red yeasts as well as Alternaria were the predominant airborne fungi, whereas, Alternaria was the dominant species associated with hay fragments. Pseudomonas, Acinetobacter and Enterobacteriaceae were the dominant Gram -ve bacteria. The most common fungal genera, such as Cladosporium and Fusarium (minor short axis), as well as Streptomyces species have an aerodynamic diameter (dae) of less than 5 microns, which can penetrate and deposit in the alveoli. Farmers and nearby residents are exposed to high levels of organic dust and bioaerosols during the wheat harvesting season. This may cause health problems in exposed persons based on toxic or allergic reactions.     

Speciation of arsenic using solid phase extraction cartridges

Various solid phase extraction (SPE) cartridges were investigated for speciation of arsenite [As(III)], arsenate [As(v)], monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). Cartridges containing different types of sorbent materials were tested for arsenic retention and elution characteristics. Alumina cartridges were found to completely retain all the four target arsenic species, and are suitable for removal and preconcentration purposes. For speciation analysis, different arsenic species were separated on the basis of their selective retention on and elution from specific cartridges. DMA was retained on a resin-based strong cation exchange cartridge and eluted with 1.0 M HCl. MMA and As(v) were both retained on a silica-based strong anion exchange cartridge and sequentially eluted with 60 mM acetic acid (for MMA) and 1.0 M HCl [for As(v)]. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently quantified by using flow injection with hydride generation atomic fluorescence spectrometry (FI-HGAFS) and hydride generation atomic absorption spectrometry (FI-HGAAS). A detection limit of 0.05 microg L(-1) arsenic in water sample was achieved using HGAFS. An application of the method was demonstrated at a drinking water treatment facility. As(III) and As(v) species were determined in water at various stages of treatment. The method is suitable for routine determination of trace levels of arsenic in drinking water to comply with more stringent environmental regulations.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

Multi-objective, decision-based assessment of a water quality monitoring network in a river system

Water quality monitoring network design has historically tended to use experience, intuition and subjective judgement in locating monitoring stations. Better design procedures to optimize monitoring systems need to simultaneously identify significant planning objectives and consider a number of social, economic and environmental constraints. The consideration of multiple objectives may require further decision analysis to determine the preference weights associated with the objectives to aid in the decision-making process. This may require the application of an optimization study to extract such information from decision makers or experts and to evaluate the overall effectiveness of locating strategies. This paper assesses the optimal expansion and relocation strategies of a water quality monitoring network using a two-stage analysis. The first stage focuses on the information retrieval of preference weights with respect to the designated planning objectives. With the aid of a pre-emptive goal programming model, data analysis is applied to obtain the essential information from the questionnaire outputs. The second stage then utilizes a weighted multi-objective optimization approach to search for the optimal locating strategies of the monitoring stations in the river basin. Practical implementation is illustrated by a case study in the Kao-Ping River Basin, south Taiwan.