Pressurised liquid-liquid extraction. An approach to the removal of inorganic non-metal species from used industrial oils

Modified pressurised hot water is used for the development of a high pressure liquid-liquid extraction method for the decontamination of used industrial oils from inorganic non-metal species (chlorine, fluorine and sulphur). The oils were subjected to dynamic extraction with water modified with 5% v/v HNO3 at 200 degrees C as extractant. Under these working conditions the analytes were transferred to the aqueous phase. Spontaneous separation of the two immiscible liquid phases (the used oil and extract) takes place in the collection flask after extraction. The treated and untreated oil samples were oxidised and the chloride, fluoride and sulphate thus formed were determined by ion-chromatography. The method was applied to four oil samples from different locations in Spain. A residence time of approximately =10 min provided oil samples from which 88.3%, 89.4% and 89.4% of chloride, fluoride and sulphate, respectively, have been removed with respect to the initial concentration of each analyte in the oil. The repeatability, expressed as relative standard deviation (RSD), was of 11.9%, 13.7% and 7.2% for Cl(-), F(-) and SO4(2-), respectively; whilst the within-laboratory reproducibility yielded RSDs of 6.2%, 7.9% and 6.2% for the same analytes. The proposed approach has proved to be efficient, simple, easily transferable to industrial scale, cheap, fast and environmentally friendly.     

Uranium-thorium disequilibrium in north-east Atlantic waters

In this paper we report and compare the concentrations of 234Th and 238U measured in surface and subsurface waters collected in the course of a sampling campaign in the north east Atlantic in June-July 1998. Dissolved 234Th concentrations in surface waters ranged from 5 to 20 Bq m(-3), showing a large deficiency relative to 238U concentrations (typically 42 Bq m-3). This disequilibrium is indicative of active 234Th scavenging from surface waters. Observed 234Th/238U activity ratios, together with corresponding 234Th particulate concentrations, were used to calculate mean residence times for 234Th with respect to scavenging onto particles (tau(diss)) and subsequent removal from surface waters (tau(part)). Residence times in the range 5-30 days were determined for tau(diss) and 4-18 days for tau(part) (n=14). In addition, ultrafiltration experiments at six stations in the course of the same expedition revealed that in north-east Atlantic surface waters a significant fraction (46+/-17%; n=6) of the thorium in the (operationally-defined) dissolved phase (<0.45 microm) is in colloidal form. These observations are consistent with the 'colloidal pumping' model in which it is assumed that 234Th is rapidly absorbed by colloidal particles, which then aggregate, albeit at a slower rate, into larger filterable particles. In essence, colloids act as intermediaries in the transition from the fully dissolved to the filter-retained (>0.45 microm) phase. Thus, the time (tau(c)) for fully dissolved 234Th to appear in the filter-retained fraction is dependent on the rate of colloidal aggregation. Here, we determined tau(c) values in the range 3-17 days.     

Global-scale vs. regional-scale scenario assumptions: implications for estimating future water withdrawals in the Elbe River basin

In this paper, we explore how scenarios of future water withdrawals in a river basin are influenced by scale-dependent quantifications of the driving forces for two global-scale storylines. Either global-scale information or region-specific information is used to do the quantifications. In addition, we analyze the impact of including or not some restricted regional-scale information in the employed water use model. To develop scenarios of water withdrawals in the German part of the Elbe River basin, we applied the modules for domestic, thermoelectric power and manufacturing water use of the global water model WaterGAP, using scale-dependent driving forces scenarios and other scale-dependent model input. In the global-scale quantitative interpretations of the storylines of the IPCC SRES scenarios A1 and B2, all major driving forces of water withdrawals in the basin—population, thermoelectric power production and industrial gross domestic product—show vigorous increases between 2000 and 2025, while from the regional perspective, smaller increases but mostly decreases appear to be plausible. These discrepancies are partly due to the fact that for the global-scale interpretations only the historic developments until 1990 were taken into account, and not until 2000 as in the regional case. The resulting scenarios of sectoral water withdrawals in 2025 differ strongly between the two scale-dependent interpretations of the storylines, with the global one leading to much higher absolute water withdrawals and much lower withdrawal decreases between 2000 and 2025. Therefore, for regional assessments of water withdrawals, we recommend to embed the scenario analysis in global-scale storylines by performing regional-scale quantifications of the global qualitative driving forces scenarios, based on a limited amount of region-specific information.     

Environmental risk assessment of phosphonates,used in domestic laundry and cleaning agents in The Netherlands

In the long-term cooperative project Voluntary Plan of Action (1990) between the Dutch Soap and Detergent Association (NVZ) and the Dutch Ministry of Housing, Spatial Planning and the Environment (VROM) environmental risk assessments of several main components of laundry cleaning formulations were completed. As a part of that project the environmental risk assessment of HEDP, ATMP, EDTMP and DTPMP phosphonates used in detergent applications has been carried out according to the EU Technical Guidance Document for Environmental Risk Assessment for New and Existing Chemicals. All PEC/PNEC ratios were well below 1. Results of this assessment based on the total industry volumes from 1995 and 1998 indicate that the environmental risk of these phosphonates is low in The Netherlands with properly functioning sewage treatment plants.     

Mapping the probability of exceeding critical thresholds for cadmium concentrations in soils in The Netherlands

The probability of exceeding critical thresholds of Cd concentrations in the soil was mapped at a national scale. The critical thresholds in soil were based on food quality criteria for Cd in crops or in organs of cattle (Bos taurus), and were calculated by inverting a regression model for the Cd concentration in the crop, with the Cd concentration in soil, soil organic matter (SOM) content, clay content, and pH as predictors. The probability of exceeding the critical threshold for Cd in soil per node of a 500- x 500-m grid was approximated by Monte Carlo simulation, using the estimated cumulative distribution functions (cdf) of SOM, clay, pH, and Cd as input. The cdfs were estimated by simple indicator kriging with local prior means. For SOM, clay, and pH, detailed maps of soil type and land use were used to define subregions with assumed constant local means of the indicators (a priori distributions). The cdfs were sampled by Latin hypercube sampling. We accounted for correlation between the actual and critical Cd concentrations in soil by drawing Cd values from cdfs conditional on SOM and clay. The estimated probability for grassland is negligible, even in areas with high Cd concentrations in soil, and for maize (Zea mays L.) land the probability is almost everywhere smaller than 5%. For arable soils, however, these probabilities commonly are larger than 5% when sugar beet (Beta vulgaris L.) or wheat (Triticum aestivum L.) is taken as a reference crop, and locally exceed 50%.     

Replacement of a multiple hearth by a fluid bed incinerator the Greensboro case history

The incinerator at the T.Z. Osborne Plant in Greensboro, North Carolina burns sludge from its own waste water treatment plant and sludge pumped from the nearby North Buffalo plant. The two plants have a combined capacity of 36 million gallons per day of wastewater. Because of the age of and increasing high maintenance on the existing multiple hearth incinerator, and the need to increase treatment capacity, the Osborne plant concluded a study in 1992 evaluating its options for future municipal sewage sludge disposal. Options which were evaluated during the study included; (i) rehabilitation of the existing eight-year old multiple hearth unit; (ii) addition of a new multiple hearth; (iii) addition of a new fluid bed system; (iv) drying, composting, or land application. The chosen option, based on both economic and environmental considerations, was a new fluid bed system with a capacity of 2.55 tons per hour, approximately double that of the existing multiple hearth. Design of the new fluid bed system began in December 1994 and equipment delivery for the incineration system was begun in April 1995. Initial operation occurred in August 1996. Primary and secondary sludge, dewatered to 28% dry solids by centrifuge, is delivered by piston pumps to the twenty-foot freeboard ID incinerator. A shell and tube heat exchanger recuperates heat from the exhaust gas and preheats the combustion air to 1250°F, resulting in minimal auxiliary fuel use. The air pollution control device is a high-energy Tandem Nozzle® scrubber. Greensboro was the initial installation of this scrubber design on a fluid bed incinerator and its characteristics and performance are discussed. Ash is dewatered in an ash thickener/belt press system prior to disposal to landfill. The system includes a state of the art Programmable Logic Controller (PLC) system for computer control of the operation. The unit was commissioned in August 1996 and has been in continuous operation since that time except for a one week inspection and maintenance shutdown in February 1999. The plant operates 24 h/day, 7 days per week. The initial performance test showed the system to readily meet federal and state air emission standards. Particulate released was 0.002 grains per dry standard cubic foot, carbon monoxide was 22.5 parts per million volumetric (ppmv) and opacity was 0.4%. These results show a significant emission reduction with the fluid bed when compared to the multiple hearth. Annual tests conducted since then and continuous emission monitoring have shown the unit to be in consistent compliance. Since the fluid bed system became operational, the old multiple hearth system has been maintained on standby as a backup, but its use has not been required. Operational experience is discussed, the most interesting of which is the relatively trouble-free operation. The minor problems which occurred and their solutions are detailed. Also included is a comparison of operation and maintenance experience of the fluid bed and the multiple hearth. Current sludge disposal actual cost data are also provided including the average cost per ton of dry solids treated. The almost three years of operational experience to date has shown that the decision to install a new fluid bed system was the correct one on both an environmental and economic basis. It has provided benefits to all interested parties — the wastewater treatment plant, the regulators, the taxpayers, and the surrounding community.