Clean Sampling and Analysis of River and Estuarine Waters for Trace Metal Studies

Most of the trace metal concentrations in ambient waters obtained a few decades ago have been considered unreliable owing to the lack of contamination ...

National Sun Yat-sen University

A one-step preconcentration method using two columns in series was used to partition trace metals in natural waters into several operationally defined fractions. The water passed through a Chelex-100 cation exchange column to collect dissolved labile trace metals and then through an AG MP-1 macroporous resin column to collect trace metals complexed with natural organic matter. A third fraction (inert) was obtained from the difference between total dissolved trace metal concentrations, determined after UV irradiation of a separate aliquot, and the sum of the fractions retained on the two columns. This analytical scheme was successfully applied to the determination of Al, Cd, Co, Cu, Fe, Mn, Ni, Pb, V, and Zn in river waters collected from across the state of Texas. Trace metal partitioning between fractions was found to be stable for at least 8 days after the addition of ammonium acetate buffer (pH 5.5). In most samples collected from relatively pristine sections of Texas rivers, the sum of fractions retained on the two columns accounted for better than 80% of the total dissolved trace metal concentrations. In rivers where anthropogenic inputs were more evident (San Antonio and Trinity Rivers), the inert fraction became pronounced, in some cases accounting for up to 95% of the total dissolved concentrations. The preconcentrate is free of matrix interference and can be easily analyzed by atomic absorption spectrometer or inductively coupled plasma mass spectrometer. Using a 1-L sample allows preconcentration factors of 150 or higher for both labile and organic fractions, and therefore, trace metal concentrations and speciation in natural waters at ambient levels can be accurately and precisely determined.

Preservation and determination of trace metal partitioning in river water by a two-column ion exchange method.

Persistent organic pollutants, POPs (e.g., polychlorinated biphenyls) can seriously and deleteriously affect environmental quality and human health. These organic pollutants are exhibiting high affinities to solid phases and thus, quickly end up in sediments. To better understand the role of carbonaceous materials in the transport and distributions of POPs in terrestrial and near-shore environments, concentrations of PCBs and carbonaceous materials (including total organic carbon, black carbon and total carbohydrates), were determined in surface sediments of the Danshui River and nearby coastal areas, Taiwan. Total concentrations of PCBs in the sediments ranged from non-detectable to 83.9 ngg(-1), dry weight, with the maximum value detected near the discharge point of the marine outfall from the Pali Sewage Treatment Plant. These results suggest that the sewage treatment plant has discharged PCBs in the past and the concentrations are still high due to their persistence; alternatively, PCBs are still being discharged in the estuarine and near-shore environment of the Danshui River. Organic carbon and black carbon concentrations correlated well with those of total PCBs in the sediments, suggesting that both organic carbon and black carbon significantly affect the distribution of trace organic pollutants through either post-depositional adsorption, or by co-transport of similar source materials. The field results demonstrate that black carbon and plays an important role in the general distribution of PCBs, while concentrations of some specific PCBs are affected by both black carbon and organic carbon concentrations.

Relationship between carbonaceous materials and polychlorinated biphenyls (PCBs) in the sediments of the Danshui River and adjacent coastal areas, Taiwan.

A vertical (laterally-averaged) two-dimensional heavy metal transport model was developed to simulate the fluxes of copper in the Danshuei River estuarine system. The toxic model was incorporated into the hydrodynamic, the salt transport and the sediment transport modules. The model has been validated with observed time series data of water surface elevation, current, salinity, and suspended sediment concentrations in 2001 and 2002. An exponential relationship was established to relate variation in partition coefficient of copper to salinity and suspended sediment concentrations in the Danshuei River estuary. Comparisons of the total, dissolved, and particulate copper concentrations calculated by the numerical model and field data along the Danshuei River-Tahan Stream show good agreement. It is noteworthy that the model requires a point source of total copper with the strength of 250 kg/day to account for the observed persistently high total copper concentration near Hsin-Hai Bridge in the Tahan Stream, about 24 km upriver from the river mouth. The huge garbage dump site near the Hsin-Hai Bridge is likely the source of heavy metal pollution. The validated model was then applied to investigate the tidally averaged salinity distributions, residual circulation, suspended sediment, and total copper concentrations under low flow condition. The residual circulation is characterized by the upriver movement of denser saline water in the lower layer and the downriver movement of fresher water in the upper layer. The circulation pattern is driven by the longitudinal gradient of salinity distribution. The residual circulation occurs in the deep channel of Kuan-Du Bridge and Taipei Bridge. Under low flow condition, the limits of salt intrusion are located at Hsin-Hai Bridge. The tidally-averaged sediment concentration distribution exhibits a local maximum concentration around the null point in the Danshuei River-Tahan Stream. A local maximum of total copper concentration, which is nearly as high as that near the point source, occurs around the null point, which is potentially a hot spot of heavy metal accumulation.

Modelling diagnosis of heavy metal (copper) transport in an estuary.

Dissolved and particulate Mn and Fe in the nearshore waters were determined at 27 stations along the west coast of Taiwan during 19-23 November 2004. The latitudinal distributions of Mn and Fe were very similar; however, the concentration in the dissolved phase was lower, whereas that in the particulate phase was higher in the northern regime. The higher percentage of Fe than Mn that was associated with particles resulted in a two-order of magnitude higher particle-water partition coefficient for Fe, K(d)(Fe), than that for Mn, K(d)(Mn). The removal fluxes of Mn and Fe could be estimated by multiplying the particulate (234)Th removal flux with the Mn/(234)Th and Fe/(234)Th ratios in suspended particles, which ranged from 0.1 to 3.8 mmol m(-2) d(-1) for Mn, and from 3.4 to 194.5 mmol m(-2) d(-1) for Fe. Residence times ranged from 1 to 20 days for Mn and Fe were estimated in the nearshore.

Removal fluxes of Mn and Fe from the nearshore waters along the west coast of Taiwan.

Vertical profiles of dissolved and particulate Mn, Fe, Ni, Cu, Zn, Cd, Pb, and (234)Th were determined in the Hung-Tsai Trough off southwestern Taiwan during 19-23 November, 2004. Except in the case of Cd, the distribution coefficient (K(d)) of the trace elements showed a negative correlation with the suspended particle concentration. Based on the average K(d) values, the general sequence of particle affinities for the eight trace elements is, from highest to lowest, Fe>Mn≈Pb>Zn≈Th>Cd≈Cu≈Ni. The trace metal data was coupled with the particle removal flux estimated from (234)Th/(238)U disequilibrium to investigate metal removal by particle sinking from the euphotic layer. The residence time of trace elements with respect to particle removal from the euphotic layer was estimated. A negative correlation between the residence time and the distribution coefficient for the trace metals was found.

Kuo-Tung Jiann

Department of Oceanography

National Sun Yat-sen University

Clean Sampling and Analysis of River and Estuarine Waters for Trace Metal Studies

Kuo-Tung Jiann

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Oceanography

National Sun Yat-sen University

Clean Sampling and Analysis of River and Estuarine Waters for Trace Metal Studies

Department of Oceanography