Risk assessment of a former military base contaminated with organoarsenic-based warfare agents: uptake of arsenic by terrestrial plants

doi:10.1016/S0048-9697(98)00400-8

Science of The Total Environment

Volume 226, Issues 2–3, 9 February 1999, Pages 237-245

https://doi.org/10.1016/S0048-9697(98)00400-8 Get rights and content

Abstract

Organoarsenic-based chemical warfare agents (CWAs) such as the sternutators diphenylchloroarsine (CLARK I), diphenylcyanoarsine (CLARK II) or phenyldichloroarsine (PFIFFIKUS) still pose a notable risk in countries where former military bases that have stored these weapons have not yet been reclaimed. In fact, this is the case for many countries of Eastern Europe and the CIS. One of the most important military bases of the former Third Reich, the Heeresmunitionsanstalt I and II, is situated close to the German–Polish border at Loecknitz (Fig. 1

). The German army stored and decanted different compounds of CWAs at this military base until 1945. When the Soviet Army destroyed the base in 1946, large amounts of CWAs and other organoarsenic compounds polluted the soil. Today up to 250 g (!) of arsenic may be found in 1 kg of soil at some places in this area. Since 1991, a Government Working Group has been working on the risk assessment in order to define the scope of reclamation measures. This study investigates the contamination and the uptake of arsenic by plants because little is known about the bioavailability and metabolism of sternutators and their constituents. The total arsenic concentration of nine different species of terrestrial plants with at least six samples per species is presented. In spite of the considerable arsenic contamination of the soil (mean value 923 mg arsenic/kg soil) the plant contamination remained comparably low. The median value of arsenic contamination of the above-ground organs of velvet grass, Holcus lanatus, was 0.7 mg/kg dry wt. and the mean value was 4.3 mg/kg dry wt. due to some highly contaminated samples. The highest arsenic concentration registered was 26 mg/kg dry wt. in a sample of H. lanatus, which was most probably caused by soil particles adhering to the plant. The chemical structure of the arsenic compounds carried by the above-ground plant organs has been determined by gas chromatographic investigations and showed an uptake of triphenyl arsine by the plants.

Introduction

The area of the former Heeresmunitionsanstalt I and II of the Third Reich is situated in the former German Democratic Republic, close to the Polish border at Loecknitz (Fig. 1). It covers an area of approximately 1 km². During 1940–1945 chemical warfare agents (CWA) such as diphenylchloroarsine (CLARK I), 2,2-dichlorodiethylsulfide (S-Lost) and a technical mixture called `Arsin oil' consisting of arsenic III chloride, diphenylchloroarsine and triphenylarsine were stored in subterranean tanks and decanted in grenades and other munition. When the Soviet Army captured the area on 26 April 1945, the tanks were filled with approximately 3000 t of these sternutators. By February 1946 the Red Army had destroyed the CWAs in order to make future use for military purposes impossible. According to depositions of witnesses and available military archives, components of chemical weapons as well as the CWAs themselves were poured into concrete basins, so-called cisterns, covered with chlorinated lime, and burnt. Pillboxes with CWA-containing tanks and subterranean pipelines were blasted. Afterwards, the whole area was secured by fences and entry was strictly prohibited. This status of no-entry-area was maintained until the reunification of the German Democratic Republic with the Federal Republic of Germany in 1990.

Since 1992, several governmental authorities have been engaged in the investigation and risk assessment of the area. The investigations carried out so far proved that soil and groundwater are contaminated with inorganic arsenic (e.g. arsenic trioxide) and different organoarsenic compounds such as CLARK I. The contamination of the soil with arsenic (inorganic arsenic and organic arsenic compounds) is very heterogeneous. Only a few feet away from so-called hot spots containing up to 250 g arsenic/kg soil, the arsenic contamination may not exceed a few mg/kg soil.

The present study deals with the contamination of wild terrestrial plants with inorganic or organic arsenic in order to evaluate the risk caused by a possible accumulation in the food chain.

Section snippets

Sampling

Samples of above-ground organs, roots and soil were collected from contaminated areas from July to September 1996. The above-ground organs were harvested by cutting approximately 1 cm above the ground and transferred into perforated plastic bags. These bags were placed into a humidified chamber (container) that was equipped with an arrestable lid and lined with a water-saturated stack of paper towels. Above-ground organs and roots were prepared for further analysis within 24 h with and without

Results

Sixteen soil samples were taken with a probe 0–40 cm under the ground surface close to the plants for arsenic analyses from five different places (Table 1). There was a wide range of scatter of the measured values caused by hot spots. However, the median value (mg arsenic/kg soil) of all samples was 840 mg/kg, the mean value was 923 mg/kg. Soil samples taken from uncontaminated sites of the same geographic area showed an arsenic background level of 10–50 mg/kg.

Altogether nine species of

Discussion

Little is known about the bioavailability and the metabolism of CWAs and their derivatives and metabolites. Burning of CWAs covered with chlorinated lime, as it was carried out after 1945, resulted in the oxidation of diphenylarsine derivatives to diphenylarsone derivatives. The diphenylcore, however, remained unchanged. Under suitable conditions, the hydrolyzed arsine derivatives may be reconverted into diphenylchloroarsine (Haas, 1996).

However, we did not find any other investigation which

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Risk assessment of a former military base contaminated with organoarsenic-based warfare agents: uptake of arsenic by terrestrial plants

Abstract

Introduction

Section snippets

Sampling

Results

Discussion

Sci Total Environ

Sci Total Environ

Sci Total Environ

Chemosphere

Effects of selected trace elements on plant growth

J Sci Food Agric

Arsenic accumulation, tolerance, and genotypic variation in plants on arsenical mine wastes in south-west England

J Plant Nutr

Arsenic speciation in the environment

Chem Rev