Barbara Radke

Analysis of Arsenic Species in Environmental Samples

Many analytical methods for determining arsenic in various forms in environmental samples have been developed in recent years. The main objective of this review article is the presentation and comparison of the three principal techniques for the determination arsenic compounds, namely: hydride generation (HG), voltammetry and chromatography (liquid chromatography including high-performance liquid chromatography (HPLC), and gas chromatography (GC). These techniques (with the exception of voltammetry) are usually coupled with numerous sensitive detectors, which gives almost unlimited possibilities for the identification of arsenic species in environmental samples. Unfortunately, every method has its own advantages and disadvantages, with the more sensitive techniques requiring complicated sample preparation involving extraction of one kind or another to concentrate the sample and eliminate the effects of the background matrix of the sample. Speciation is the most important requirement for analysis in environmental research and HPLC is the most powerful method for arsenic species.

The content of butyl-and phenyltin derivatives in the sediment from the Port of Gdansk

Harbor sediments containing large deposits of organotin compounds constitute a potential threat to the marine environment. Samples of harbor sediments were collected twice in the years 2003 and 2005 from the following locations: Ziółkowskiego, Siarkowe, Wiślane, Weglowe, Chemików and Paliw Płynnych Quays. The cores of 25cm length sliced into 2- and 5-cm segments were analyzed. After drying and homogenization, samples were split into two granulometric fractions, i.e. <2.00 and <0.063mm. The dominant fraction in whole sediment, i.e. fraction grain diameter <2.00mm, was sand (grain diameter 2.00-0.063mm). However, the highest concentrations of butyltin (BT) and phenyltin (PT) compounds were found in the fine sediment fraction. The mean values of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) in the analyzed samples in the <2.00mm fraction were 2144.9, 434.7 and 148.1ngSng(-1)d.w., respectively, while the corresponding mean values in the <0.063mm fraction were 6556.4, 1593.7 and 450.0ngSng(-1)d.w. The mean concentrations of monophenyltin (MPhT) have been estimated at 29.0 and 49.9ngSng(-1)d.w. for the <2.00 and <0.063mm fraction sizes, respectively. The estimated content levels of diphenyltin (DPhT) and triphenyltin (TPhT) were in most cases below the detection limit of the applied method. The sediment cores collected from the locations characterized by high industrialization and intense exploitation (Wiślane, Weglowe Quays) contained the highest concentrations of BT and PT.

Seasonal changes in organotin compounds in water and sediment samples from the semi-closed Port of Gdynia.

The effect of seasonal changes on the distribution of organotin compounds (OTC) in the sediments and seawater from the docks of the Port of Gdynia was investigated. Sediment and seawater samples were collected from four industrial docks in February (winter) and June (summer) in 2009. The samples were analyzed for butyltin, phenyltin, octyltin, and tricyclohexyltin (total of 9 OTC derivatives). The fine fraction (<0.063 mm) accumulated the highest concentration of OTC, although it was not the dominant fraction in the sediment samples from the Port of Gdynia. The average concentration of TBT, DBT and MBT in collected samples were as follows: 4400; 2188; 730 ng cation g⁻¹ d.w. (February) 3638; 1590; 474 ng cation g⁻¹ d.w. (June) in the fine sediment samples, 2805; 1266; 485 ng cation g⁻¹ d.w. (February) in <2.00 mm sediment fractions and 118.6; 39.2; 25.3 ng cation L⁻¹ (February) and 46.5; 12.6; 8.2 ng cation L⁻¹ (June) in the water samples. Higher concentrations of butyltin derivatives (BT) were observed in samples collected in February than in those collected in June. Seasonal changes in BT correlate well with changes in the water pH and concentrations of organic matter and can be attributed to sorption/desorption to sediments, photodegradation and biodegradation. Although the Port of Gdynia does not represent the natural features of a marine environment, seasonal variations recorded in the pH values as well as BT, organic carbon and biogenic element concentrations seem to be influenced by temperature and microbial activity.

The Speciation of Organotin Compounds in Sediment and Water Samples from the Port of Gdynia

Organotin compounds (OTC) are toxic towards all living organisms. The application of organitin-based antifouling systems is becoming the main source of OTC in the ocean. Harbor sediments and water contain large deposits of organotin compounds due to application of antifouling systems in the shipping industry. OTC contamination presents a potential risk to the marine environment. Sediment and water samples were collected in 2009 from Gdynia Harbor. For all the analyzed organotin compounds, the mean concentration values were determined: water samples monobutyltin (MBT): 13.2, dibutyltin (DBT): 16.7, tributyltin (TBT): 60.7 (ng cation dm−3), and sediment samples MBT: 261.4, DBT: 751.9, TBT: 2148.2 (ng cation g−1 d.w.). The estimated content of monophenyltin (MPhT), diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOT), dioctyltin (DOT), and tricyclohexyltin (TCHT) were below the detection limit of the applied method. It was found that the content of organic matter, the amount of fine fraction, and the pH all play a significant role in the distribution and sorption process of OTC between the water and the sediment on the bottom. Compared to an earlier study, the concentrations of all OTC are much lower, confirming that the applied legislation has had a positive impact.

Analytical methods and problems related to the determination of organotin compounds in marine sediments

The determination of organotin compounds in bottom sediments is a complex process that requires a number of analytical steps, i.e. sample collection, transport and storage; extraction of analytes from sediment; derivatization; extract purification; enrichment; and the final chromatographic measurement. The whole process is time and labour consuming, and subject to securing sample representativeness. In this review the most frequently encountered problems and the examples of possible analytical solutions are presented, which encompass the specific steps of speciation analysis of these toxic compounds.

Distribution of migration (state) forms of microelements in the sediments of the ports of Klaipėda and Gdańsk

Distribution of migration (state) forms of microelements in the sediments of the ports of Klaipėda and Gdańsk During investigations of the Baltic Sea basin significant differences have become manifest in the distribution of certain chemical elements in different chains of the geo (-eco) system (soils, river, lagoon and marine sediments). This paper presents data on the quantitative relationships of elements resulting from interactions of natural sedimentation processes and the possible human impact on the sediments from two port areas. The total (T), lithogenic (LG; stable) and hydrogenic (HG; mobile, reactive) migration forms of Zn, Cr, Cd, Cu, Pb and Ni were analysed. The HG component comprises that pool of the elements contained in readily degrading minerals; increases in this form potentially being an indicator of adverse human impacts. The distribution of total forms depends on the quantity of the sediment fraction with grain size < 0.063 mm (fr. < 0.063 mm) and on the concentration of organic content (Corg). With increasing sediment depth, the concentration of elements decreases sharply, although HG concentrations were seen to increase on several occasions. One explanation for such findings is the mineralisation and decomposition of metals from the remnants of biological activities of organisms (pellets, globules) into the sediments. Element concentrations in the natural sedimentation zone (NSZ) of the marine-influenced North Port at Gdańsk are less than in the NSZ and technogenic sedimentation zone (TSZ) of the riverine part of the port of Gdańsk. The ratios between HG, LG and T in the two sedimentation zones are different for different elements, but are always higher in the TSZ than in the NSZ. Multi-site analyses of the port basins allowed NSZ and TSZ to be distinguished. The TSZ is typified by anomalous concentrations of elements, the specific distribution of their migration forms, the semi-stagnant conditions prevailing there and the proximity of human impact sources. The data presented in this paper indicate that the concentrations of only some of the elements in the TSZ sediments of the ports of Klaipėda and Gdańsk exceed the permitted norms for spoil dredged from port basins. By no means can the total load of elements contained in the spoil dumped at sea be treated as an indicator of marine pollution. For an objective assessment of the real pollution threat to port environments, detailed investigations of the various migration forms of chemical elements need to be carried out, and previously established levels revised.

Arsenic-Based Warfare Agents: Production, Use, and Destruction

Since the beginning of time, civilizations have looked for more creative ways to dominate and defeat their enemies. The rapid development of the chemical industry just before the Second World War started the era of modern chemical weapon production based on poisons, including toxic arsenic compounds. This paper provides a detailed overview of the production, usage and destruction of this dangerous chemical weapon. Milestones include: (i) the development of knowledge concerning the synthesis and decomposition of toxic warfare agents containing arsenic compounds, (ii) increased awareness of the influence of this poison on human life and the environment, (iii) the development of modern technology for the destruction of chemical weapons, (iv) implementation of legislation which prohibits the use of chemical weapons in combat, and (v) the development of analytical methods to detect arsenic compounds in the environment that was used in warfare. The article includes events before World War I and next focuses on World War II, the Vietnam War and the two Gulf Wars. It further details the development of specific arsenical chemical weapons (e.g. Lewisite, Clark I, Clark II, Adamsite), as well as some agents used as herbicides, like Agent Blue. Special attention is paid to the disarmament times and the challenges of implementing a world-wide plan to destroy chemical weapon stockpiles.

Aspects of Pollution in Gdansk and Gdynia Harbours at the Coastal Zone of the South Baltic Sea

Organotin compounds (OTC), as well as metals, are toxic to many organisms. Even at very low concentrations OTC and metals can have several negative effects. The paper discusses key issues relating to the location of harbours in the coastal zone (including near the river mouths and semi-closed access to the sea) and the pollution of harbour sediments with heavy metals (e.g. zinc, copper, nickel and lead) and organotin derivatives (e.g. butyltin, phenyltin, octyltin, and tricyclohexyltin), using the examples of the Gdansk and Gdynia ports. The authors have described key spatial factors of the two ports which largely determine sedimentation processes. It has been shown that the heavy metals content in the sediments of the Port of Gdansk does not exceed the concentration values permitted by Polish law, however, the problem with the establishment of standard concentration levels for organotin derivatives remains.

Spatial distribution of labile and total forms of copper and zinc in sediments from the Port of Gdansk

Spatial distribution of labile and total forms of copper and zinc in sediments from the Port of Gdansk Sediment cores were collected from a number of sites in the Port of Gdansk in 1997 and 1998. The samples were segregated by depth then dried, homogenised and sieved into four grain size fractions (>2.00 mm, 2.00 - 0.063 mm, 0.063 - 0.032 mm, and 0.032 mm) Small-grained sand with a low admixture of silt predominated in all samples, whilst the amount of organic matter and water varied between samples. The 2.00 - 0.063 mm size fraction was the most abundant; and also showed the highest accumulation of trace metals. In the >2.00 mm size fraction the mean concentration of labile forms of copper was 9.06 mg kg-1 DW, while the concentration of total forms was 12.73 mg kg-1 DW. The mean concentrations of labile and total forms of zinc in this fraction were 31.79 and 46.27 mg kg-1 DW, respectively. The widest ranges of concentrations for both labile and total forms of the metals were found in the near-surface sediment layers (0-20 cm). Sediments collected from highly industrialized locations contained the highest concentrations of metals.