Chlorination of soil organic matter: The role of humus type and land use.

The levels of natural organic chlorine (Clorg) typically exceed levels of chloride in most soils and is therefore clearly of high importance for continental chlorine cycling. The high spatial variability raises questions on soil organic matter (SOM) chlorination rates among topsoils with different types of organic matter. We measured Clorg formation rates along depth profiles in six French temperate soils with similar Cl deposition using 36Cl tracer experiments. Three forest sites with different humus types and soils from grassland and arable land were studied. The highest specific chlorination rates (fraction of chlorine pool transformed to Clorg per time unit) among the forest soils were found in the humus layers. Comparing the forest sites, specific chlorination was highest in mull-type humus, characterized by high microbial activity and fast degradation of the organic matter. Considering non-humus soil layers, grassland and forest soils had similar specific chlorination rates in the uppermost layer (0-10 cm below humus layer). Below this depth the specific chlorination rate decreased slightly in forests, and drastically in the grassland soil. The agricultural soil exhibited the lowest specific chlorination rates, similar along the depth profile. Across all sites, specific chlorination rates were correlated with soil moisture and in combination with the patterns on organic matter types, the results suggest an extensive Cl cycling where humus types and soil moisture provided best conditions for microbial activity. Clorg accumulation and theoretical residence times were not clearly linked to chlorination rates. This indicates intensive Cl cycling between organic and inorganic forms in forest humus layers, regulated by humic matter reactivity and soil moisture, while long-term Clorg accumulation seems more linked with overall deep soil organic carbon stabilization. Thus, humus types and factors affecting soil carbon storage, including vegetation land use, could be used as indicators of potential Clorg formation and accumulation in soils.

Chlorine cycling and the fate of Cl in terrestrial environments.

Chlorine (Cl) in the terrestrial environment is of interest from multiple perspectives, including the use of chloride as a tracer for water flow and contaminant transport, organochlorine pollutants, Cl cycling, radioactive waste (radioecology; 36Cl is of large concern) and plant science (Cl as essential element for living plants). During the past decades, there has been a rapid development towards improved understanding of the terrestrial Cl cycle. There is a ubiquitous and extensive natural chlorination of organic matter in terrestrial ecosystems where naturally formed chlorinated organic compounds (Clorg) in soil frequently exceed the abundance of chloride. Chloride dominates import and export from terrestrial ecosystems while soil Clorg and biomass Cl can dominate the standing stock Cl. This has important implications for Cl transport, as chloride will enter the Cl pools resulting in prolonged residence times. Clearly, these pools must be considered separately in future monitoring programs addressing Cl cycling. Moreover, there are indications that (1) large amounts of Cl can accumulate in biomass, in some cases representing the main Cl pool; (2) emissions of volatile organic chlorines could be a significant export pathway of Cl and (3) that there is a production of Clorg in tissues of, e.g. plants and animals and that Cl can accumulate as, e.g. chlorinated fatty acids in organisms. Yet, data focusing on ecosystem perspectives and combined spatiotemporal variability regarding various Cl pools are still scarce, and the processes and ecological roles of the extensive biological Cl cycling are still poorly understood.

Influence of Multiple Environmental Factors on Organic Matter Chlorination in Podsol Soil.

Natural chlorination of organic matter is common in soils. The abundance of chlorinated organic compounds frequently exceeds chloride in surface soils, and the ability to chlorinate soil organic matter (SOM) appears widespread among microorganisms. Yet, the environmental control of chlorination is unclear. Laboratory incubations with 36Cl as a Cl tracer were performed to test how combinations of environmental factors, including levels of soil moisture, nitrate, chloride, and labile organic carbon, influenced chlorination of SOM from a boreal forest. Total chlorination was hampered by addition of nitrate or by nitrate in combination with water but enhanced by addition of chloride or most additions including labile organic matter (glucose and maltose). The greatest chlorination was observed after 15 days when nitrate and water were added together with labile organic matter. The effect that labile organic matter strongly stimulated the chlorination rates was confirmed by a second independent experiment showing higher stimulation at increased availability of labile organic matter. Our results highlight cause-effect links between chlorination and the studied environmental variables in podsol soil-with consistent stimulation by labile organic matter that did overrule the negative effects of nitrate.

Chlorination and dechlorination rates in a forest soil - A combined modelling and experimental approach.

Much of the total pool of chlorine (Cl) in soil consists of naturally produced organic chlorine (Clorg). The chlorination of bulk organic matter at substantial rates has been experimentally confirmed in various soil types. The subsequent fates of Clorg are important for ecosystem Cl cycling and residence times. As most previous research into dechlorination in soils has examined either single substances or specific groups of compounds, we lack information about overall bulk dechlorination rates. Here we assessed bulk organic matter chlorination and dechlorination rates in coniferous forest soil based on a radiotracer experiment conducted under various environmental conditions (additional water, labile organic matter, and ammonium nitrate). Experiment results were used to develop a model to estimate specific chlorination (i.e., fraction of Cl(-) transformed to Clorg per time unit) and specific dechlorination (i.e., fraction of Clorg transformed to Cl(-) per time unit) rates. The results indicate that chlorination and dechlorination occurred simultaneously under all tested environmental conditions. Specific chlorination rates ranged from 0.0005 to 0.01 d(-1) and were hampered by nitrogen fertilization but were otherwise similar among the treatments. Specific dechlorination rates were 0.01-0.03d(-1) and were similar among all treatments. This study finds that soil Clorg levels result from a dynamic equilibrium between the chlorination and rapid dechlorination of some Clorg compounds, while another Clorg pool is dechlorinated more slowly. Altogether, this study demonstrates a highly active Cl cycling in soils.

Experimental evidence of large changes in terrestrial chlorine cycling following altered tree species composition.

Organochlorine molecules (Clorg) are surprisingly abundant in soils and frequently exceed chloride (Cl(-)) levels. Despite the widespread abundance of Clorg and the common ability of microorganisms to produce Clorg, we lack fundamental knowledge about how overall chlorine cycling is regulated in forested ecosystems. Here we present data from a long-term reforestation experiment where native forest was cleared and replaced with five different tree species. Our results show that the abundance and residence times of Cl(-) and Clorg after 30 years were highly dependent on which tree species were planted on the nearby plots. Average Cl(-) and Clorg content in soil humus were higher, at experimental plots with coniferous trees than in those with deciduous trees. Plots with Norway spruce had the highest net accumulation of Cl(-) and Clorg over the experiment period, and showed a 10 and 4 times higher Cl(-) and Clorg storage (kg ha(-1)) in the biomass, respectively, and 7 and 9 times higher storage of Cl(-) and Clorg in the soil humus layer, compared to plots with oak. The results can explain why local soil chlorine levels are frequently independent of atmospheric deposition, and provide opportunities for improved modeling of chlorine distribution and cycling in terrestrial ecosystems.