Maris Klavins

Heavy metals in rivers of Latvia

Total heavy metal concentrations in waters and sediments (HNO3 digestible Pb, Cu, Co, Ni, Mn, Zn) and their speciation forms in sediments (exchangeable, carbonate bound, iron-manganese oxide bound, organic matter bound and residual) in major and common small watercourses (31 sampling stations) along their flow in Latvia were determined. The metal loads entering the Baltic Sea from Latvia were calculated. Increased metal concentrations were found only in lower reaches of the largest rivers and locally around known industrial pollution sources. Differences in metal concentrations and loads in rivers from different regions of Latvia were related to natural geochemical processes. Metal speciation analysis showed that the dominant metal species are residual metals and those bound to organic matter. Residual and carbonate-bound metal dominated only in rhitral regions of rivers. The concentrations of exchangeable metals increased below pollution sources.

Immobilisation of humic substances

Attempts were made to immobilise humic substances (HS) by grafting them onto different carriers (styrene-divinylbenzene copolymers, cellulose and silica) as well as by their crosslinking with formaldehyde. Reaction with Merrifield resin was used for the immobilisation of HS, coupling by means of water-soluble carbodiimides to carriers containing amino-groups. Crosslinking of HS with formaldehyde (also in presence of other substances able to enter polycondensation reactions with formaldehyde) was shown to be an efficient method for their insolubilisation. Properties of the obtained immobilised HS were studied, including their potential use as sorbents for several metal ions and organic substances. The adsorption efficiency was found to depend both on the sorbate used, type of humic substance immobilised and character of the polymeric matrix. Immobilised HS can be regarded as a prospective sorbents for the removal of different organic molecules and metals ions from the aquatic environment.

Highlighting inconsistencies regarding metal biosorption

Thousands of articles have been devoted to examine different types of biosorbents and their use in cleaning polluted waters. An important objective of some studies has been the identification of the biosorption mechanisms. This type of investigation is not always performed, as it can only be done if scientists are aware of all mechanisms that, at least theoretically, control the removal of the target substances. Mistakes are often made, even in highly cited review articles, where biosorption mechanisms are named and/or grouped. The aim of this article is to highlight errors and inaccuracies as well as to discuss different classification systems of the biosorption mechanisms. This article serves as a guide, as well as a platform for discussion among researchers involved in the investigation of biosorbents, in an effort to avoid reproducing errors in subsequent articles.

Sorption of humic substances on aquifer material at artificial recharge of groundwater

Experiments in batch equilibrium system were carried out to evaluate the importance of physical and chemical factors determining the sorption efficiency of humic substances (HS) on aquifer material, which has been used for artificial recharge of groundwater (ARG) in drinking water production. Results showed that an increase of the amount of clay in the aquifer material and a decrease of pH in water increased the sorption efficiency. The sorption of higher molecular weight, more hydrophobic and aromatic HS (Aldrich and forest soil humic acids) were greater than the sorption of acidic HS (river fulvic acids), either on the aquifer material or to its representative sorbing phases, clay and organic matter. The sorption on the aquifer material was largely due to physical sorption (hydrophobic attractions). This study showed the importance of HS composition on their removal during ARG and contributed to an understanding of the HS sorption mechanisms in this process.

Sedimentary humic substances from lakes in Latvia

Humic and fulvic acids, isolated from sediments of lakes in different trophic states (Latvia) were studied. The humic substances (HS) were characterized by their elemental and functional composition, their spectral properties, and molecular mass. The humus properties strongly depend on the origin of the sedimentary HS. Substantial similarity between sedimentary HS from oligotrophic and dystrophic water bodies was found, unless the biology of these lakes greatly differs. Humic molecules from sediments of oligotrophic and dystrophic lakes are smaller, more uniform, and contain lower amounts of carboxyl- and hydroxyl-groups than HS from meso- and eutrophic water bodies. On the other hand, sedimentary HS from meso- and eutrophic lakes are dominated by aliphatic structures, and, possibly chromophore groups are present, and they are rich in polar groups. The macromolecules of HS from meso- and eutrophic lakes show the highest polydispersity.

Characterisation of humic substances by acid catalysed transesterification

Abstract The chemical composition of low molecular weight moieties linked to the core structures of humic substances (HS) are of substantial importance for the understanding of the chemical structures and mode of interactions of HS with other substances in the environment. In this study a novel approach to characterise certain low molecular weight compounds bound to HS is suggested. The method includes transesterification (TE) of ester and amide bound structures, and esterification (E) of free carboxylic groups using acid catalysed methanolysis followed by gas chromatography (GC)–mass spectrometry (MS) and GC-FID analysis. Methanolysis of five HS of different origin, demonstrated the presence of multifunctional hydroxy-substituted benzoic acids, hexoses, and long chain fatty acids. Based on GC-FID and addition of the internal standard before methanolysis, the total amounts of low molecular weight material could be estimated. In case of HS from the aqueous sources the yields were below 1%, whereas in case of the HS derived from lignite the yield was significantly higher. The hydrophobic long chain fatty acids constituted about one-third of this material. Principal component analysis (PCA), which was used for extended data evaluation, differentiated between the samples in terms of chemical composition.

Assessment of the changes of cod and color in rivers of Latvia during the last twenty years

Analysis of long-term records of the concentrations of water color and chemical oxygen demand for nine river sites in Latvia is reported. The period of observations lasted for the last 20 years. Characteristic features of data include non-normal distributions, serial correlation, seasonality and presence of mostly significant downward trends. In Latvia, the main water quality changes could be explained by the changes of anthropogenic impact and the type of catchment management over the last 20 years.

Trends of natural organic matter concentrations in river waters of Latvia

This study revealed significant (P < 0.1and P < 0.05) increasing trends of total organic carbon (TOC) and water colour in most of the studied Latvian rivers during the last decade. However, over longer time periods, there were pronounced oscillations of TOC concentrations, similar to patterns of long-term changes of river discharge regime. On a yearly basis, there was a positive correlation between parameters of organic matter concentration and discharge in all selected rivers (rS = 0.540–0.803; P < 0.01). The impact of discharge on concentrations of organic matter could be masked by other factors, such as changes in precipitation, biological processes, soil types or land use.

Decarboxylation and alkaline colour fading reactions in presence of humic substances

Humic substances (HSs) can substantially influence velocity of reactions in the environment as shown on example of decarboxylation and alkaline colour (e.g., malachite green and crystal violet) fading reactions. In colour fading and decarboxylation reactions of 6-nitrobenzisoxazole-3-carboxylic acid HS act as inhibitors, but additions of surfactants change the pattern of reaction. The inhibitory activity of HSs much depends on their origin. The velocity of studied reactions depends also on pH, temperature and concentration of HS used. Possible micellar catalysis mechanism has been suggested.

Evaluation of plankton communities in small highly humic bog lakes in Latvia

This paper reports the results of a study performed at the Teici State Reserve in Latvia The results indicated that algal communities in brown water lakes were formed by species that were tolerant to a low pH and high humic substance concentration. The composition of the species of phytoplankton and zooplankton was comparatively simple. A significant correlation was found between the number of species of phytoplankton, zooplankton, and the pH value. Similarly there was a clear relationship between the taxonomic composition of phytoplankton, zooplankton, and the trophic state of the lakes. Dyseutrophic lakes were characterized by comparatively higher biodiversity of planktonic communities than dystrophic lakes. There was also a correlation between humic substance concentration and total bacterial numbers, and humic substance concentration and total number of zooplankton, respectively. The composition of the species, the biomass of phytoplankton and zooplankton, as well as the numbers of bacterioplankton, were specific for humic lakes and could assist in the identification of the unaffected state of bog lakes ecosystems.