A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.     

Interpretation of roadside PM10 monitoring data from Sunderland,United Kingdom

Roadside PM₁₀ has been monitored by Partisol® at three sitesin Sunderland between August 1997 and February 1998. The sites chosen were an inner city kerbside site; a roadside site adjacentto a dual carriageway on the outskirts of Sunderland with an openaspect; and a rural site.The results indicate that there is a seasonal variation in the relationship between the sites in terms of monitored PM₁₀.In the winter there is a poor correlation between the sites whereas in the summer significant correlations are obtained. Of the sites monitored PM₁₀ is consistently highest at the inner city roadside site. During the summer, exceedances of theU.K. 50 g m^-3 standard (DETR, 2000) are associated with conditions suitable for the build-up of photochemical pollutionhowever during the winter period exceedances are recorded duringa variety of weather conditions.At the dual carriageway site PM_2.5 has also been recorded and contributions to measured PM₁₀ are 77% in summer and68% in winter. The results illustrate a number of inconsistencies between this study utilising the Partisol® andothers reporting results where PM₁₀ has been monitored by TEOM®.     

Trihalomethanes in Drinking Water of Greater Québec Region (Canada): Occurrence, Variations and Modelling

The levels of trihalomethanes (THMs) – the main species of by-product from water chlorination – were monitored in thedistribution systems of the five major drinking water utilitiesof the greater area of Québec City in order to investigate andmodel their occurrence on a spatial and seasonal basis. Data forTHMs and other water quality and operational parametersassociated with their formation were generated through a 16 monthsampling program involving several sites representing variablewater residence times, from the plant to the system extremity.The results demonstrate that the differences in measured THMlevels between the five utilities are mainly due to the variablequality of raw waters, the type of water treatment process beingused and the type and levels of applied disinfectant. Dependingon the utility, average THM levels were from 1.3 to 2.5 timeshigher in the system extremities than in the water leaving thetreatment plant. Also, average levels of THMs measured in summerat the distribution system extremities were, depending on theutility, from 2.5 to 5 times higher than the average levelsmeasured in winter. The seasonal differences were found to besignificantly greater than those observed by others in waterutilities in the United States and Europe and are explained inlarge part by the considerable changes, over the year, in thequality and temperature of surface waters in Southern Québec. Forthe five utilities under study, multivariate regression modelswere developed in order to predict spatial and seasonalvariations of THMs. Both residual chlorine demand and temperaturewere found to be better, statistically, as predictors for THMoccurrence. The usefulness of the developed models for routineand long term water quality management, as well as for assessmentof human exposure to THMs, are also discussed.     

Determination of organophosphorus pesticides and related compounds in water samples by membrane extraction and gas chromatography

A membrane extraction-gas chromatography method was developed fordetermination of organophosphorus pesticides and related compounds including methamidophos, DDVP, dimethoate, methyl parathion, parathion, thiophosphoric acid trimethyl ester, and thiophosphoramidic acid dimethyl ester in water samples. In thismethod, surface-modified acetic cellulose membranes were used to extract the target analytes in water samples, the extracted analytes were back-extracted into a small amount of methanol, andgas chromatography with pulsed flame photometric detector (GC-PFPD) was used to determine the concentrations of targetanalytes in the extracts. The recoveries obtained for thetarget analytes spiked into the water samples ranged from 66to 94%. The method detection limit for each target analyte was 0.05 g L^-1. The method developed in this study had shown the advantages of being cheap, simple, fast, and reliable. It had been used successfully to determine the concentrations of target analytes in river water samples.     

Competitive Retention of Lead and Cadmium on an Agricultural Soil

Lead and cadmium contamination of an agricultural soil has been studied using batch and column experiments. Thermodynamics of theretention phenomena may be represented by a Langmuir isotherm foran aqueous metal concentration up to 100 mg L^-1. First order kinetics with respect to the solid phase yield good predictabilityfor both batch and column experiments. Kinetics and thermodynamics of lead retention predominate over those ofcadmium. As a consequence, lead is preferentially retainedand can even displace sorbed cadmium. In the event of anspill involving both metals, cadmium would move further inthe soil and its aqueous concentration downstream could beeven higher than that of the influent solution, increasingpotential risks. A two-region model has been used to fit all the experimental results. Satisfactory predictions for column experiments are obtained with parameters which are consistent with those obtained for the batch experiments, for which sorption is described by a Langmuir isotherm including competitive retention.     

Status and Trends of Dissolved Oxygen in Corpus Christi Bay, Texas, U.S.A.

The purpose of this studywas to determine status and long-term trends of dissolved oxygen concentrations (DO) in Corpus Christi Bay, Texas, U.S.A. A 20-year record of randomized stations was used to determine the trend of surface water DO, salinity, and temperature over space and time. A 13-year record of two fixed stations was used to determine the temporal nutrient trends. A 10-year record of fixed stations in the southeastern region of Corpus Christi Bay was used to determine the status of disturbance caused by low DO in bottom waters. From 1982 to 2002, there was a significant decrease in surface water DO at a rate of 0.06 mg L⁻¹ yr⁻¹ and a significant increase in surface water temperature at a rate of 0.07°C yr⁻¹. The southeastern region of Corpus Christi Bay had the lowest average DO, and during July and August, DO are steadily declining at a rate of 0.09 mg L⁻¹ yr⁻¹. It is not likely that eutrophication is causing hypoxia, because freshwater inflow rates have significantly decreased since 1941 and nutrient levels have not changed from 1987 to 2000. Even though long-term trends indicate that average surface DO is decreasing, disturbance by hypoxia appears to be stable, but this may be due to just eight years of data. In fact, if the current trend continues, surface water DO will not meet exceptional aquatic life standards (≤5 mgL⁻¹) in 2032.     

Ecological Risk Assessment of Abandoned Shrimp Ponds in Southern Thailand

The potential ecological risks associated with contaminants from 15 abandoned shrimp ponds in southern Thailand were assessed at the screening level. Shrimp ponds reported as out of production for more than 2 years were selected as sampling sites. The assessment endpoint was identified as the protection of aquatic life from hazard of multiple agents or stressors in water or sediment from the ponds. The measurement endpoints were amount of toxic phytoplankton species, Yellow Head Viruses, SEMB viruses, oxytetracycline, cadmium, copper, and manganese. Data from field measurements and laboratory analyses obtained primarily from April to June 2003 were used in the risk analysis. The results showed that insignificant amounts of stressors were present, except for the metals. So, only concentration values of the metals were used in the calculation of hazard quotients (HQ) for risk characterization. The highest potential ecological risk characterized by the highest HQ value observed for each metal was 19 for manganese, 4.3 for cadmium, and 1.8 for copper. These findings indicated a need for further ecological risk assessment at a more detailed level to focus on the bioavailability and effects of metals from abandoned shrimp farms, with manganese the highest priority.     

Sulphate, Nitrogen and Base Cation Budgets at 21 Forested Catchments in Canada, the United States and Europe

To assess the concern over declining base cation levels in forest soils caused by acid deposition, input-output budgets (1990s average) for sulphate (SO₄), inorganic nitrogen (NO₃-N; NH₄-N), calcium (Ca), magnesium (Mg) and potassium (K) were synthesised for 21 forested catchments from 17 regions in Canada, the United States and Europe. Trend analysis was conducted on monthly ion concentrations in deposition and runoff when more than 9 years of data were available (14 regions, 17 sites). Annual average SO₄ deposition during the 1990s ranged between 7.3 and 28.4 kg ha⁻¹ per year, and inorganic nitrogen (N) deposition was between 2.8 and 13.8 kg ha⁻¹ per year, of which 41–67% was nitrate (NO₃-N). Over the period of record, SO₄ concentration in deposition decreased in 13/14 (13 out of 14 total) regions and SO₄ in runoff decreased at 14/17 catchments. In contrast, NO₃-N concentrations in deposition decreased in only 1/14 regions, while NH₄-N concentration patterns varied; increasing at 3/14 regions and decreasing at 2/14 regions. Nitrate concentrations in runoff decreased at 4/17 catchments and increased at only 1 site, whereas runoff levels of NH₄-N increased at 5/17 catchments. Decreasing trends in deposition were also recorded for Ca, Mg, and K at many of the catchments and on an equivalent basis, accounted for up to 131% (median 22%) of the decrease in acid anion deposition. Base cation concentrations in streams generally declined over time, with significant decreases in Ca, Mg and K occurring at 8, 9 and 7 of 17 sites respectively, which accounted for up to 133% (median 48%) of the decrease in acid anion concentration. Sulphate export exceeded input at 18/21 catchments, likely due to dry deposition and/or internal sources. The majority of N in deposition (31–100%; median 94%) was retained in the catchments, although there was a tendency for greater NO₃-N leaching at sites receiving higher (<7 kg ha^-1 per year) bulk inorganic N deposition. Mass balance calculations show that export of Ca and Mg in runoff exceeds input at all 21 catchments, but K export only exceeds input at 16/21 sites. Estimates of base cation weathering were available for 18 sites. When included in the mass balance calculation, Ca, Mg and K exports exceeded inputs at 14, 10 and 2 sites respectively. Annual Ca and Mg losses represent appreciable proportions of the current exchangeable soil Ca and Mg pools, although losses at some of the sites likely occur from weathering reactions beneath the rooting zone and there is considerable uncertainty associated with mineral weathering estimates. Critical loads for sulphur (S) and N, using a critical base cation to aluminium ratio of 10 in soil solution, are currently exceeded at 7 of the 18 sites with base cation weathering estimates. Despite reductions in SO₄ and H⁺ deposition, mass balance estimates indicate that acid deposition continues to acidify soils in many regions with losses of Ca and Mg of primary concern. The U.S. Government's right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged. The Canadian Crown reserves the right to retain a non-exclusive, royalty free licence in and to any copyright.     

Extractive Spectrofluorometric Determination of Quinalphos Using Fluorescein in Environmental Samples

A simple, sensitive, convenient and low cost spectrofluorometric technique for determination of quinalphos is described. Quinalphos is decomposed with sodium ethoxide. Resultant sodium diethyl thiophosphate (Na-DETP) is extracted with a cationic fluorescein as ion pair complex into 1-chloro-2-nitrobenzene. The fluorescence of the ion pair, fluorescein-DETP is measured at 530 nm after excitation at 490 nm. This technique is applicable for the determination of quinalphos in water, food grains and vegetable samples up to ng level with Amberlite XAD-4.     

Evaluation of Water Quality in the Chillán River (Central Chile) Using Physicochemical Parameters and a Modified Water Quality Index

The Chillán River in Central Chile plays a fundamental role in local society, as a source of irrigation and drinking water, and as a sink for urban wastewater. In order to characterize the spatial and temporal variability of surface water quality in the watershed, a Water Quality Index (WQI) was calculated from nine physicochemical parameters, periodically measured at 18 sampling sites (January–November 2000). The results indicated a good water quality in the upper and middle parts of the watershed. Downstream of the City of Chillán, water quality conditions were critical during the dry season, mainly due to the effects of the urban wastewater discharge. On the basis of the results from a Principal Component Analysis (PCA), modifications were introduced into the original WQI to reduce the costs associated with its implementation. WQI_DIR2 and WQI_DIR, which are both based on a laboratory analysis (Chemical Oxygen Demand) and three (pH, temperature and conductivity), respectively, four field measurements (pH, temperature, conductivity and Dissolved Oxygen), adequately reproduce the most important spatial and temporal variations observed with the original index. They are proposed as useful tools for monitoring global water quality trends in this and other, similar agricultural watersheds in the Chilean Central Valley. Possibilities and limitations for the application of the used methodology to watersheds in other parts of the world are discussed.