Rates of Abiotic MnII Oxidation by O2: Influence of Various Multidentate Ligands at High pH.

Oxidation of manganous manganese (MnII) is an important process driving manganese cycles in natural aquatic systems and leading to the formation of solid-phase MnIII,IV (hydr)oxide products. Previous research has shown that some simple ligands (e.g., phosphate, sulfate, chloride, fluoride) can bind with MnII to make it unreactive to oxidation by dissolved oxygen. However, there is little to no understanding of the role played by stronger, complex-forming ligands in MnII oxidation reactions. The objective of this study was to evaluate the rates of abiotic MnII oxidation by O2 in the presence of low concentrations of several complex-forming model ligands (pyrophosphate, tripolyphosphate, ethylenediaminetetraacetic acid, oxalate) in bicarbonate-carbonate buffered laboratory solutions of pH 9.42, 9.65, and 10.19. The influence of increasing ligand concentrations on observed autocatalytic profiles of MnII oxidation was investigated, and initial oxidation rates were linked quantitatively to the initial MnII speciation in experimental solutions. Observed rates of MnII oxidation decreased with increasing ligand concentration for all four ligands tested. However, the profiles observed with time and the magnitudes of decrease in initial oxidation rates were different for the different ligands. Likely explanations for these observations include the denticity of the tested ligands, the relative strength of the ligands to complex MnII versus MnIII, and the ability of some ligands to enhance the reduction of MnIII back to MnII on a time scale comparable to the forward homogeneous MnII oxidation reaction.

Establishing of monitoring network on Kosovo Rivers: preliminary measurements on the four main rivers (Drini i Bardhë, Morava e Binqës, Lepenc and Sitnica).

The main goal of this work was to suggest to authorities concerned a monitoring network on main rivers of Kosovo. We aim to suggest application of WFD (Water Framework Directive) in Kosovo as soon as possible. Our present chemical research could be the first step towards it, giving an opportunity to plan the monitoring network in which pollution locations will be highlighted. In addition to chemical, future ecological studies could be performed. Waters of the rivers Drini i Bardhë, Morava e Binçës, Lepenc and Sitnica, which are of supra-regional interest, are investigated systematically along the river course. Sediments of these rivers were also investigated at the same monitoring points and results have recently been published by us. In this paper we present results of mass concentrations of eco-toxic metals: Cu(II), Pb(II), Cd(II), Zn(II) and Mn(II) in waters of four main rivers of Kosovo, using Anodic Stripping Voltammetry (ASV), Atomic Absorption Spectrophotometry (AAS) and Ultraviolet-Visible (UV-VIS) Spectrometry. Also some physico-chemical parameters are determined: water temperature, electrical conductivity, pH, alkalinity, total hardness and temporary hardness. Results of concentrations of eco-toxic metals in water are compared with concentrations found in sediments at the same locations. Statistical methods are applied to determine anomalous regions Classification of waters at each sampling station of our work was tentatively performed based on metal indicators, using Croatian standards. Our results are showing that concentrations of Zn in all waters are low and pose no risk for living organisms. Exception is water at S5 station, where concentration is above permanent toxic level. Concentrations of Pb and Mn are high at D5 station on Drini i Bardhë River (14 km from boarder to Albania) and at all stations along Sitnica River. Cadmium in high concentrations which is above permanent toxic level is measured in water only at two stations, one (M1) on Morava e Binçës River and the other (S5) on Sitnica River (56 km from boarder to Serbia). Comparison with available results from the past shows that water pollution with respect to toxic elements decreased since 1989, what is explained with closing of heavy industry since then. Continuation of water and sediment monitoring using more than one experimental technique is highly recommended, particularly at locations S2 and S5 with anomalous concentrations of toxic elements, as well as establishing of permanent network of monitoring stations by Kosovo authorities. Remediation of sediments at polluted locations in Sitnica River would be desirable.

Levels of elements in the surficial estuarine sediments of the Hugli River, northeast India and their environmental implications.

The present paper is the first document of a detailed geochemical and mineralogical study of muddy to sandy mud estuarine sediments of the Hugli River collected from five different sites along its course in the coastal areas of West Bengal, northeast India. The present work attempts to establish the status of distribution and environmental implications of 52 elements in the surficial estuarine sediments and their possible sources of derivation. The level of both metallic and non-metallic elements shows a wide range of variation all along the course of the estuary and can be attributed to their differential derivation from the source rocks and differential discharge of untreated effluents originating from industrial, agricultural, aquacultural as well as domestic sewage. The element contents, particularly the heavy metal content in the sediments, are the lowest in the upstream part of the estuary at Diamond Harbor, whereas, these are slightly higher in the intermediate stretch of the estuary at Haldia to highest in the mouth of estuary at Gangasagar. These changes indicate that the metals that are carried from upstream find their ultimate depositional sink at the delta mouth near Gangasagar, where almost all the elements showed elevated values. The majority of the elements have their highest concentrations at Canning, a site within the tidal channel network of the Hugli-Matla drainage basin away from the direct influence of the Hugli River. This site is severely contaminated with huge organic load from domestic sewage, aquaculture, intensive trawling activities and agricultural runoff. Moreover, the site suffers from heavy siltation load causing an almost moribund condition of Matla River at this point. Equi-dimensional quartzo-feldspathic mineral grains are consistent components in the siliciclastic composition of the sediments and their sizes at each station are controlled by respective hydrodynamic conditions. Various flaky minerals (mica, chlorite, hornblende) are also present but show inconsistent patterns of distribution. These flaky minerals remain in suspension for a long time and do not follow the usual law of settling of particles depending on the hydrodynamic regime prevailing in the area. Presented data will serve as a baseline against which future anthropogenic effects may be assessed. A comprehensive account of heavy metal content in sediments from different coastal regions of peninsular India has also been presented for purpose of comparison.

A comparison of anthropogenic mercury pollution in Kastela Bay (Croatia) with pristine estuaries in Ore (Sweden) and Krka (Croatia).

Anthropogenic mercury pollution was studied in Kastela Bay (Croatia), 10 years after chloralkaline plant (PVC) stopped production. The concentration of total mercury determined in sediments which are composed mainly of calcite and quartz, are in the range 14,280-30,400 ng/g. The values are higher than reported in the literature for Elbe and Seine estuaries and also above 25,000 ng/g used for criterion in remediation project in Minamata Bay. The concentration of methylmercury 6.05-36.74 ng/g are typical for slightly to highly contaminated estuarine sediments. The low ratio of methylmercury to total mercury found in sediments of Kastela Bay is in the range 0.04-0.18%. It can be explained that in this region predominate conditions which do not promote in-situ methylation. Sediments were found to be highly anoxic. Concentrations of total mercury in unfiltered surface waters are in the range 69-145 ng/l and in unfiltered bottom waters in the range 230-1,418 ngl(-1). High concentrations found in bottom waters suggest that either resuspension or partial dissolution of sediments takes place. An experiment performed on filtered and unfiltered waters showed that about 85% of total mercury in surface water and almost 100% in bottom water was retained on 45 microm filters. To demonstrate contrasts, two pristine estuaries from norths and south Europe were studied. Silicious sediments of Ore estuary (Sweden) and calcareous sediments of Krka estuary (Croatia) have total mercury concentrations close to accepted background level. The ratio of methylmercury to total mercury is < or = 1% in all samples with one exception. The highest observed ratio (2.70%) was in the surface sediment from E2 station in Krka estuary measured in March 2000. This location is suitable for studying methylmercury formation in pristine environment.