Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.     

210Po bioaccumulation in coastal sand dune wild legumes--Canavalia spp. of southwest coast of India

In view of considerable natural background radioactivity reported from southwest coast of India, the current study documents bioaccumulation of 210Po in two dominant coastal sand dune perennial mat-forming wild legumes, Canavalia cathartica and C. maritima. Root, stem, leaf, mature beans, dry seeds and rhizosphere sand were analyzed for 210Po concentration. 210Po activity decreased in the order of leaves > roots > seeds > stems > beans. The highest 210Po activity was recorded in rhizosphere sand samples (5.78-5.88 Bq kg(-1)) followed by the leaf samples (3.27-3.07 Bq kg(-1)), while it was lowest in mature beans (0.13-0.20 Bq kg(-1)). 210Po activities or tissue moisture between plant species were not significantly different (p > 0.05; t-test). But 210Po activity vs. moisture differed significantly in all tissues (p = 0.0001), vegetative tissues (root, stem and leaf) (p = 0.0016), seeds (p = 0.0393) and proteins in seeds (p = 2.355 x 10(-6)) indicating the importance of moisture and protein in 210Po accumulation. Although 210Po has affinity for proteins, it did not concentrate too much in seed proteins of Canavalia. Concentration of 210Po in mature beans is at safe levels as fisher folk only consume tender pods occasionally. 210Po activity in Canavalia is compared with other plant materials. As the landraces of C. cathartica and C. maritima are distributed throughout pantropical coastal areas, the current study emphasizes on considering them as bioindicators to monitor 210Po in coastal sand dune biomes and in turn the health of coastal population.     

The study of age influence on human bone lead metabolism by using a simplified model and X-ray fluorescence data

Long term lead metabolism in the human body has never been fully understood due to the lack of human data in this area. The technological improvement of bone lead measurement systems has made bone lead data of substantial populations available. In this study, a set of X-ray fluorescence bone lead data was used to test Leggett's lead metabolism model (R. W. Leggett, Environ. Health Perspect., 1993a, 101, 598-616), especially the model of metabolism in bone. The data set includes the bone lead concentration of 539 occupationally exposed workers, of whom 327 were measured twice in five years. The bone lead concentrations of both cortical bone (tibia) and trabecular bone (calcaneus) were obtained by Cd-109 gamma-ray induced XRF measurement. The histories of blood lead concentration for these workers were used to regulate the input file of the model. The results show that the bone lead concentrations predicted by Leggett's model greatly underestimate the measured values, especially for older workers. This data set was then organized into five age groups. A new simplified model was applied to estimate the lead transfer rates between blood and lead compartments for these age groups. The original transfer rates and the new transfer rates are compared, and the differences are discussed. When the transfer rates derived from measured bone lead data were put into the input file of the model to replace the existing parameters, the predicted values were much closer to the measured values for both cortical bone and trabecular bone.     

Interlaboratory evaluation of endotoxin analyses in agricultural dusts--comparison of LAL assay and mass spectrometry

Endotoxin exposure is associated with wheeze and asthma morbidity, while early life exposure may reduce risk of allergy and asthma. Unfortunately, it is difficult to compare endotoxin results from different laboratories and environments. We undertook this study to determine if lipopolysaccharide (LPS) extraction efficiency could account for differences among laboratories. We generated and collected aerosols from chicken and swine barns, and corn processing. We randomly allocated side-by-side filter samples to five laboratories for Limulus assay of endotoxin. Lyophilized aliquots of filter extracts were analyzed for 3-hydroxy fatty acids (3-OHFAs) as a marker of LPS using gas chromatography-mass spectrometry. There were significant differences in endotoxin assay and GC-MS (LPS) results between laboratories for all dust types (p < 0.01). Patterns of differences between labs varied by dust type. Relationships between assay and GC/MS results also depended on dust type. The percentages of individual 3-OHFA chain lengths varied across labs (p < 0.0001) suggesting that each lab recovered a different fraction of the LPS available. The presence of large amounts of particle associated LPS and absence of a freezing thawing cycle were associated with lower correlations between LPS and bioactivity, consistent with an absence of Limulus response to cell-bound endotoxin. These data suggest that extraction methods affect endotoxin measurements. The LAL methods may be most suitable when comparing exposures within similar environments; GC-MS offers additional information helpful in optimizing sample treatment and extraction. GC-MS may be of use when comparing across heterogeneous environments and should be considered for inclusion in future studies of human health outcomes.     

EPA's monitoring program at Love Canal 1980

Summary As stated at the beginning of this paper conclusions reached thus far cannot be discussed in this paper. However, a great deal of information is available for examination.EPA displayed its ability to coordinate widely separated laboratories, both Federal and private, into a smooth working team in a very short period of time. A very comprehensive study plan was also developed and implemented quickly. EPA was fortunate to have already had GCA under contract when the emergency arose. In no small part the success of the field effort was due to the managerial and technical abilities of the GCA team.Within a period of 6 weeks a plan was developed, a prime contractor retained, subcontractors hired, and field activities begun. Within a period of 3 months in excess of 8600 field samples were collected and over 12,000 field and QC samples were analyzed. During this same period 2 major data systems were developed, debugged, and placed into operation.In short this EPA project was probably the most comprehensive multimedia field project ever attempted by EPA and certainly the data is being subjected to the most strenuous quality control measures ever imposed by this Agency. The entire program is presently under peer review and the results are being prepared for publication by EPA Headquarters.Note. Originally intended to be published as part of the special issue on Exposure Monitoring: An International Workshop (Las Vegas, Nevada, October 19–22, 1981).     

Influence of aluminium on the restoration potential of a terrestrial vascular plant,Portulaca Oleracea L. as a biomonitoring tool of fresh water aquatic environments

In the present study, the influence of aluminium on the regeneration potential of leaf and stem-cuttings of Portulaca oleracea was studied in order to identify a terrestrial plant species as an alternate biomonitoring toolof fresh water environment. The leaves and stem cuttings of theterrestrial plant, P. oleracea grew well in the distilled water producing adventitious and lateral roots. The aluminium treated leaves and stem cuttings showed a reduction in the growthof the adventitious and lateral roots and increase in the decay of leaves and stem cuttings with increasing aluminium concentration. The tolerance index calculated for the leaves and the stem cuttings showed that the leaves were more sensitivethan stems to aluminium. Since all the parameters studied showedconcentration dependent changes, the terrestrial plant, P. oleracea can be considered a suitable biomonitoring tool of fresh water environment besides its usage in the Al toxicity testing.     

The Variability of Estimates of Variance, and Its Effect on Power Analysis in Monitoring Design

Power analysis can be a valuable aid in the design of monitoringprograms. It requires an estimate of variance, which may come from a pilot study or an existing study in a similar habitat. For marine benthic infauna, natural variation in abundances canbe considerable, raising the question of reliability of varianceestimates. We used two existing monitoring programs to generatemultiple estimates of variance. These estimates were found to differ from nominated best estimates by 50% or more in 43% of cases, in turn leading to under or over-estimation of samplesize in the design of a notional monitoring program. The twostudies, from the same general area, using the same samplingmethods and spanning a similar time scale, gave estimatesvarying by more than an order of magnitude for 25% of taxa.We suggest that pilot studies for ecological monitoring programsof marine infauna should include at least two sampling times.     

Large-scale mercury variations in Lake Vänern (Sweden) 1974-98

Lake V?nern, the largest lake in Sweden, has been seriously contaminated with mercury during the 20th century. In the 1970's and 80's the direct load, mainly from a chlor-alkali industry in the area, of mercury was drastically reduced as a response to new legislation, from three to five tons down to between five and ten kg yr(-1). Large amounts of the disposed pollutant have accumulated in the sediments. The question posed in this work is now, is the effect of the drastic load reduction after more than two decades visible in the sediments? The question is relevant as large areas still are blacklisted for fishing, but also as a follow-up of a major remedy action. The lake also serves as a freshwater reservoir for even Sweden's second largest city. This work synthesises and compares data of mercury in the sediments from three major field programs, in 1974, 1984 and 1998. The interest is focused on both spatial heterogeneity and temporal trends. In 1974, the surface concentrations are significantly higher than in subsequent surveys. Significant differences are also found between 1984 and 1998. Significant spatial differences within the lake are found for respective year. The most contaminated area is located in the north, close to the major point source (a former chlor-alkali industry). This is also the area with the largest improvement, as a direct response to the reduction in load. Further from the outlet, the recovery is more affected by burial and transport processes out into the deeper basins.     

Simultaneous determination of parathion and p-nitrophenol in vegetable tissues by derivative spectrophotometry

A first derivative spectrophotometric method has been developedfor the determination of parathion and p-nitrophenol in vegetabletissues. Ethanol was used as solvent for extracting the compoundsfrom the tissues and subsequently the samples were evaluated against a vegetable tissue blank, directly by derivative spectrophotometry. The simultaneous determination of these compounds can be carried out using the zero-crossing approach for parathion at 253.0 nm and for p-nitrophenol at 273.1 nm. In the samples each analyte was determined in the presence of one another in the ranges between 4.9 to 3883.5 g g^-1 forparathion and 4.9 to 3285.3 g g^-1 for p-nitrophenol.The detection limits (3) were found to be 1.5 and 1.4 g g^-1 for parathion and p-nitrophenol, respectively. The relative standard deviations were in all instances less than1.8%. The proposed method was applied to the determination ofthe analytes in spiked leafs of corn. The results show a goodrecovery and they are in agreement with those obtained bypolarography.     

Response of the Ascorbate-Peroxidase of Selenastrum capricornutum to Copper and Lead in Stormwaters

The green alga Selenastrum capricornutum expresses a uniqueascorbate peroxidase, that responds to copper and lead. Attemptswere made to test if this peroxidase could be used to monitor thelevels of copper and lead in natural waters. When S.capricornutum was exposed to a stormwater sample, the specificactivity of the peroxidase in the cell extract was commensuratewith the combined copper and lead contents in the sample. Theperoxidase responses were also correlated with the 96 hr biomasstoxicity assay of S. capricornutum. However, unlike thebiomass toxicity assay, the peroxidase activity was not affectedby the anions in the samples. The use of this peroxidase can beused as a marker for testing heavy metal toxicity in the water.