KALMAN FILTERING FOR RESOLUTION OF OVERLAPPING LINES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

A Kalman filter was developed for resolving overlapping lines in inductively coupled plasma atomic emission spectrometry (ICP-AES) and evaluated experimentally with the determination of La in the presence of Ho, and Cu in the presence of Pr. The whiteness of the innovation sequence for an optimal filter was explored to be the criterion for the correction of the wavelength positioning errors which may occur in spectral scans. Under the conditions of the medium-resolution spectrometer and 1.5 pm step size in scans, the filter effectively resolved the Cu/Pr line pair having a small peak separation of 4.8 pm. For the La/Ho line pair with a peak distance of 9.8 pm, an unbiased estimate for La concentration was still obtained even when the signal-to-background ratio was down to 0.048. Favourable detection limits for real samples were achieved. Unstructured backgrounds were modeled theoretically and all spectral scans therefore did not require the correction for solvent.

EVALUATION OF THE RELIABILITY OF KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This paper deals with the evaluation of the reliability of the analytical results obtained by Kalman filtering. Two criteria for evaluation were compared: one is based on the autocorrelation analysis of the innovation sequence, the so-called NAC criterion; the other is the innovations number, which actually is the autocorrelation coefficient of the innovation sequence at the initial wavelength. Both criteria allow compensation for the wavelength positioning errors in spectral scans, but there exists a difference in the way they work. The NAC criterion can provide information about the reliability of an individual result, which is very useful for the indication of unmodelled emissions, while the innovations number should be incorporated with the normalization of the innovations or seek the help of the sequence itself for the same purpose. The major limitation of the NAC criterion is that it does not allow the theoretical modelling of continuous backgrounds, which, however, is convenient in practical analysis and can be taken with the innovations number criterion.

EVALUATION OF THE EFFECT OF WAVELENGTH POSITIONING ERRORS ON KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This work evaluates the effect of wavelength positioning errors in spectral scans on analytical results when the Kalman filtering technique is used for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a positioning accuracy of 0.1 pm is required in order to obtain accurate and precise estimates for analyte concentrations. The positioning error in sample scans is more crucial than that in model scans. The relative bias in measured analyte concentration originating from a positioning error in a sample scan increases linearly with an increase in the magnitude of the error and the peak distance of the overlapping lines, but is inversely proportional to the signal-to-background ratio. By the use of an optimization procedure for the positions of scans with the innovations number as the criterion, the wavelength positioning error can be reduced and, correspondingly, the accuracy and precision of analytical results improved.

Density-dependent effects on seston dynamics and rates of filtering and biodeposition of the suspension-cultured scallop Chlamys farreri in a eutrophic bay (northern China): An experimental study in semi-in situ flow-through systems

Effects of stocking density on seston dynamics and filtering and biodeposition by the suspension-cultured Zhikong scallop Chlamys farreri Jones et Preston in a eutrophic bay (Sishili Bay, northern China), were determined in a 3-month semi-field experiment with continuous flow-through seawater from the bay. Results showed that the presence of the scallops could strongly decrease seston and chlorophyll a concentrations in the water column. Moreover, in a limited water column, increasing scallop density could cause seston depletion due to scallop's filtering and biodeposition process, and impair scallop growth. Both filtration rate and biodeposition rate of C. farreri showed significant negative correlation with their density and positive relationship with seston concentration. Calculation predicts that the daily removal of suspended matter from water column by the scallops in Sishili Bay ecosystem can be as high as 45% of the total suspended matter; and the daily production of biodeposits by the scallops in early summer in farming zone may amount to 7.78 g m(-2), with daily C, N and P biodeposition rates of 3.06 x 10(-1), 3.86 x 10(-2) and 9.80 x 10(-3) g m(-2), respectively. The filtering and biodeposition by suspension-cultured scallops could substantially enhance the deposition of total suspended particulate material, suppress accumulation of particulate organic matter in water column, and increase the flux of C, N and P to benthos, strongly enhancing pelagic-benthic coupling. It was suggested that the filtering-biodeposition process by intensively suspension-cultured bivalve filter-feeders could exert strong top-down control on phytoplankton biomass and other suspended particulate material in coastal ecosystems. This study also indicated that commercially suspension-cultured bivalves may simultaneously and potentially aid in mitigating eutrophication pressures on coastal ecosystems subject to anthropogenic N and P loadings, serving as a eutrophic-environment bioremediator. The ecological services (e.g. filtering capacity, top-down control, and benthic-pelagic coupling) functioned by extractive bivalve aquaculture should be emphasized in coastal ecosystems. (c) 2005 Elsevier B.V. All rights reserved.

Influence of filtering and biodeposition by the cultured scallop Chlamys farreri on benthic-pelagic coupling in a eutrophic bay in China

In coastal ecosystems, suspension-cultured bivalve filter feeders may exert a strong impact on phytoplankton and other suspended particulate matter and induce strong pelagic-benthic coupling via intense filtering and biodeposition. We designed an in situ method to determine spatial variations in the filtering-biodeposition process by intensively suspension-cultured scallops Chlamys farreri in summer in a eutrophic bay (Sishili Bay, China), using cylindrical biodeposition traps directly suspended from longlines under ambient environmental conditions. Results showed that bivalve filtering-biodeposition could substantially enhance the deposition of total suspended material and the flux of C, N and P to the benthos, indicating that the suspended filter feeders could strongly enhance pelagic-benthic coupling and exert basin-scale impacts in the Sishili Bay ecosystem. The biodeposition rates of 1-yr-old scallops varied markedly among culture sites (33.8 to 133.0 mg dry material ind.(-1) d(-1)), and were positively correlated with seston concentrations. Mean C, N and P biodeposition rates were 4.00, 0.51, 0.11 mg ind.-1 d-1, respectively. The biodeposition rates of 2-yr-old scallops were almost double these values. Sedimentation rates at scallop culture sites averaged 2.46 times that at the reference site. Theoretically, the total water column of the bay could be filtered by the cultured scallops in 12 d, with daily seston removal amounting to 64%. This study indicated that filtering-biodeposition by suspension-cultured scallops could exert long-lasting top-down control on phytoplankton biomass and other suspended material in the Sishili Bay ecosystem. In coastal waters subject to anthropogenic N and P inputs, suspended bivalve aquaculture could be advantageous, not only economically, but also ecologically, by functioning as a biofilter and potentially mitigating eutrophication pressures. Compared with distribution-restricted wild bivalves, suspension-cultured bivalves in deeper coastal bays may be more efficient in processing seston on a basin scale.