The formation and fate of chlorinated organic substances in temperate and boreal forest soils

Background, aim and scope  Chlorine is an abundant element, commonly occurring in nature either as chloride ions or as chlorinated organic compounds (OCls). Chlorinated organic substances were long considered purely anthropogenic products; however, they are, in addition, a commonly occurring and important part of natural ecosystems. Formation of OCls may affect the degradation of soil organic matter (SOM) and thus the carbon cycle with implications for the ability of forest soils to sequester carbon, whilst the occurrence of potentially toxic OCls in groundwater aquifers is of concern with regard to water quality. It is thus important to understand the biogeochemical cycle of chlorine, both inorganic and organic, to get information about the relevant processes in the forest ecosystem and the effects on these from human activities, including forestry practices. A survey is given of processes in the soil of temperate and boreal forests, predominantly in Europe, including the participation of chlorine, and gaps in knowledge and the need for further work are discussed. Results  Chlorine is present as chloride ion and/or OCls in all compartments of temperate and boreal forest ecosystems. It contributes to the degradation of SOM, thus also affecting carbon sequestration in the forest soil. The most important source of chloride to coastal forest ecosystems is sea salt deposition, and volcanoes and coal burning can also be important sources. Locally, de-icing salt can be an important chloride input near major roads. In addition, anthropogenic sources of OCls are manifold. However, results also indicate the formation of chlorinated organics by microorganisms as an important source, together with natural abiotic formation. In fact, the soil pool of OCls seems to be a result of the balance between chlorination and degradation processes. Ecologically, organochlorines may function as antibiotics, signal substances and energy equivalents, in descending order of significance. Forest management practices can affect the chlorine cycle, although little is at present known about how. Discussion  The present data on the apparently considerable size of the pool of OCls indicate its importance for the functioning of the forest soil system and its stability, but factors controlling their formation, degradation and transport are not clearly understood. It would be useful to estimate the significance and rates of key processes to be able to judge the importance of OCls in SOM and litter degradation. Effects of forest management processes affecting SOM and chloride deposition are likely to affect OCls as well. Further standardisation and harmonisation of sampling and analytical procedures is necessary. Conclusions and perspectives  More work is necessary in order to understand and, if necessary, develop strategies for mitigating the environmental impact of OCls in temperate and boreal forest soils. This includes both intensified research, especially to understand the key processes of formation and degradation of chlorinated compounds, and monitoring of the substances in question in forest ecosystems. It is also important to understand the effect of various forest management techniques on OCls, as management can be used to produce desired effects.     

Formation of chloroacetic acids from soil,humic acid and phenolic moieties

The mechanism of formation of chloroacetates, which are important toxic environmental substances, has been controversial. Whereas the anthropogenic production has been well established, a natural formation has also been suggested. In this study the natural formation of chloroacetic acids from soil, as well as from humic material which is present in soil and from phenolic model substances has been investigated. It is shown that chloroacetates are formed from humic material with a linear relationship between the amount of humic acid used and chloroacetates found. More dichloroacetate (DCA) than trichloroacetate (TCA) is produced. The addition of Fe(2+), Fe(3+) and H(2)O(2) leads to an increased yield. NaCl was added as a source of chloride. We further examined the relationship between the structure and reactivity of phenolic substances, which can be considered as monomeric units of humic acids. Ethoxyphenol with built-in ethyl groups forms large amounts of DCA and TCA. The experiments with phenoxyacetic acid yielded large amounts of monochloroacetate (MCA). With other phenolic substances a ring cleavage was observed. Our investigations indicate that chloroacetates are formed abiotically from humic material and soils in addition to their known biotic mode of formation.     

Vertical distribution of organochlorine pesticides in humus along Alpine altitudinal profiles in relation to ambiental parameters

In forest soils along vertical profiles located in different parts of the Alps, concentrations of persistent organic pollutants (POPs), namely organochlorine pesticides (OCPs) like dichlorodiphenyltrichloroethanes (DDTs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), heptachlor, aldrin, dieldrin and mirex, were measured. Though local characteristics of the sites are influenced by numerous factors like orographic and meteorological parameters, forest stand characteristics and humus parameters, we ascertained a marked vertical increase of concentrations of some organochlorine compounds in the soil. On the basis of climatological values of each site, we found that the contamination increase with altitude can be ascribed to a certain ‘cold condensation effect’. In addition, the perennial atmospheric deposition of POPs is controlled by precipitation. Other key parameters explaining the accumulation of POPs are the soil organic carbon stocks, the turnover times, the re-volatilisation and degradation processes, which vary with altitude.     

Biogeochemistry of mercury in the Amazonian environment

In this paper, the processes that affect mercury (Hg) cycling in the Amazonian environment were reviewed, criticized and new directions of research are proposed. The discussion of the origin of the mercury contamination, whether natural or anthropogenic is marked by a lack of fundamented arguments from both sides. Undoubtedly mercury inputs from gold mining have locally increased environmental concentrations, but in the whole Amazon, these loads would be insignificant, considering the high concentrations observed by some authors in remote soils. A reasonable process that should explain these elevated concentrations in soil is that B horizons function as a mercury "sponge" that have been accumulating mercury over a geological time scale, releasing it back to cycling during erosion and forest fires. The environmental degradation of the Amazonian forest due to human activities is probably enhancing the release of that mercury to the cycle. Mercury transformations in reduced, anoxic environments--sediments and waters--are also a key problem for the understanding of the environmental methylation. The studies that have been carried out in the Amazonian environment are too restricted and results permit only circumstantial conclusions. Large efforts must be directed to monitoring programs considering time and space variability.     

Geographical distribution of persistent organochlorines in air, water and sediments from Asia and Oceania, and their implications for global redistribution from lower latitudes

Persistent organochlorines in air, river water and sediment samples were analysed from eastern and southern Asia (India, Thailand, Vietnam, Malaysia, Indonesia) and Oceania (Papua New Guinea and Solomon Islands) to elucidate their geographical distribution in tropical environment. The concentrations of organochlorines in these abiotic samples collected from Taiwan, Japan and Australia were also monitored for comparison. Atmospheric and hydrospheric concentrations of HCHs (hexachlorocyclohexanes) and DDTs (DDT and its metabolites) in the tropical developing countries were apparently higher than those observed in the developed nations, suggesting extensive usage of these chemicals in the lower latitudes. CHLs (chlordane compounds) and PCBs (polychlorinated biphenyls) were also occasionally observed at higher levels in the tropics, implying that their usage area is also expanding southward. Distribution patterns of organochlorines in sediments showed smaller spatial variations on global terms, indicating that the chemicals released in the tropical environment are dispersed rapidly through air and water and retained less in sediments. The ratios of organochlorine concentrations in sediment and water phases were positively correlated with the latitude of sampling, suggesting that persistent and semivolatile compounds discharged in the tropics tend to be redistributed on a global scale.     

Organochlorine pesticides and hexachlorobenzene in tissues of fish and invertebrates caught near a sewage outfall

Concentrations of organochlorine pesticides and hexachlorobenzene (HCB) were determined in 16 fish, 1 mollusc and 1 crustacean species living near a cliff-face sewage outfall. For the 15 organochlorine compounds scanned, HCB, chlordane, dieldrin and SigmaDDT were recorded in highest concentrations. There was considerable variation in concentrations between muscle and liver and between species. Livers had higher concentrations of organochlorines and a higher percentage lipid than muscle. The highest concentrations were recorded in livers of the elasmobranch and tetraodontiform fishes. Organochlorines were only recorded at low concentrations in muscle, often at or near detection limits. No organochlorines were detected in the two invertebrate species.     

Organochlorines and endometriosis: a mini-review

Organochlorines (polychlorinated biphenyls and dioxin-like compounds) are suspected to play a role in the etiopathogenesis of endometriosis. This hypothesis, based on experimental data, has been circulating for years in the scientific community and several epidemiologic surveys have attempted to obtain confirmatory human data. The purpose of this mini-review is to provide an overview of the twelve epidemiological studies that have assessed the relationship between endometriosis and organochlorine exposure. Several studies did not observe a significant association between peritoneal endometriosis and organochlorines. The deep nodular form of endometriosis appears associated with a higher serum level of both dioxin-like compounds and polychlorobiphenyls. The type of control women, the nature of the chemicals measured, and the definition of the disease could modulate the ability to detect the possible relationship between endometriosis and organochlorine exposure.     

Presence and biomagnification of organochlorine pollutants and heavy metals in mammals of Do?ana National Park (Spain), 1982-1983

The existence of 11 organochlorine compounds and five heavy metals in the liver and muscle of 57 members of 10 species of mammals, all from Do?ana National Park (Spain), has been investigated. Five organochlorine compounds have been found and the five heavy metals were present in the samples. The biomagnification of organochlorines is shown. The detected concentrations for each trophic rank seem not to influence unfavourably on the population stability of the species. The rabbit is proposed as a monitor species for future studies in pollution at Do?ana National Park.     

Two decades of experimental manipulations of heaths and forest understory in the subarctic

Current atmospheric warming due to increase of greenhouse gases will have severe consequences for the structure and functioning of arctic ecosystems with changes that, in turn, may feed back on the global-scale composition of the atmosphere. During more than two decades, environmental controls on biological and biogeochemical processes and possible atmospheric feedbacks have been intensely investigated at Abisko, Sweden, by long-term ecosystem manipulations. The research has addressed questions like environmental regulation of plant and microbial community structure and biomass, carbon and nutrient pools and element cycling, including exchange of greenhouse gases and volatile organic compounds, with focus on fundamental processes in the interface between plants, soil and root-associated and free-living soil microorganisms. The ultimate goal has been to infer from these multi-decadal experiments how subarctic and arctic ecosystems will respond to likely environmental changes in the future. Here we give an overview of some of the experiments and main results.     

Organochlorine contaminants in the estuarine and coastal marine environments of the Fiji Islands

No information has been published on the presence of organochlorine pesticides and polychlorinated biphenyls in the Fiji Islands. This paper reports the first data on the concentration of a range of organochlorine compounds in sediments and shellfish in the estuarine and coastal marine environment around Fiji. Twenty-three sediment and two shellfish samples were analysed for 22 pesticides and related residues, and PCBs. While a significant number of organochlorines (20 pesticide related species and PCBs) was detected, the concentrations were generally very low (< 10 ng g), indicative of a relatively 'less contaminated' marine environment. Relatively high concentrations were observed only near the two major ports (Suva and Lautoka), with Suva harbour samples having the largest number of detectable species and the largest total concentrations of organochlorines (up to 91 ng g). No PCBs were detected in areas away from major industrial centres. The variations in the concentrations found, and the possible sources and movement of the organochlorine contaminants are discussed.     

Resembling a “natural formation pattern” of chlorinated dibenzo-p-dioxins by varying the experimental conditions of hydrothermal carbonization

Until several years ago dioxins were considered as just an unwanted by product of anthropogenic activities and stigmatized as the symbol of man-made environmental pollution. Natural processes, such as forest fires, can emit dioxins, but compared to industrial processes, usually very low quantities are emitted. However after a case of food contamination occurred in the United States of America in 1996 caused by kaolinitic clay a discussion on the provenience started. Besides the relatively high concentration also an unusual PCDD/F distribution pattern was found in these ball clay samples. This specific pattern related to none of the known anthropogenic sources for these contaminants and, in relation to a supposed natural formation, later it was named “natural formation pattern”. Hydrothermal carbonization (HTC) can transform biomass within hours into a brown coal-like product which resembles naturally occurring coal formation. HTC can also transform an already present PCDD/F contamination in a way to obtain a “natural formation pattern” characterized by an unusual high ratio between 1,2,3,7,8,9-HxCDD and 1,2,3,6,7,8-HxCDD and the absence of almost all chlorinated dibenzofurans. By varying the experimental conditions of the HTC process applied to sewage sludge samples contaminated with PCDD/Fs from anthropogenic sources, beside the “natural formation pattern” at a temperatures of 255 °C, a remarkable increase of the toxicity based on WHO–TEQ was observed.     

Formation of organochlorine compounds in kraft pulp bleaching processes

The most abundant volatile organochlorine compounds (VOCCs), trichloroacetic and dichloroacetic acids and AOX, were determined in bleaching effluent and waste water from three kraft pulp mills during ClO₂ bleaching. 0.6–7.7 g of VOCCs per ton bleached pulp were formed, the most abundant being chloroform and dichloroacetic acid methyl ester. Most of the VOCCs were removed during treatment, and it was estimated that 2–30 t of VOCCs would be removed annually from activated sludge treatment plants in Finnish kraft pulp mills using elemental chlorine free bleaching, most likely by volatilization. Dichloroacetic acid was formed in considerably higher amounts than trichloroacetic acid, and both compounds were removed effectively during treatment. The formation of all organochlorine compounds decreased considerably when non-chlorinated bleaching was employed.     

Formation of chloroform in spruce forest soil--results from laboratory incubation studies

The release of chloroform, 1,1,1-trichloroethane, tetrachloromethane, trichloroethene and tetrachloroethene from an organic rich spruce forest soil was studied in laboratory incubation experiments by dynamic headspace analysis, thermodesorption and gas chromatography. Performance parameters are presented for the dynamic headspace system. For spruce forest soil, the results showed a significant increase in chloroform concentration in the headspace under aerobic conditions over a period of seven days, whereas the concentration of the other compounds remained fairly constant. A biogenic formation of chloroform is suggested, whereas for the other compounds anthropogenic sources are assumed. The addition of trichloroacetic acid to the soil increased the release of chloroform from the soil. It is, therefore, suggested that trichloroacetic acid also contributed to the formation of chloroform. Under the experimental conditions, the spruce forest soil released chloroform concentrations corresponding to a rate of 12 microg m(-2) day(-1). Data on chloroform production rates are presented and compared with literature results, and possible formation mechanisms for chloroform are discussed.     

Modeling and Spatially Distributing Forest Net Primary Production at the Regional Scale

Abstract

Forest, agricultural, rangeland, wetland, and urban landscapes have different rates of carbon sequestration and total carbon sequestration potential under alternative management options. Changes in the proportion and spatial distribution of land use could enhance or degrade that area’s ability to sequester carbon in terrestrial ecosystems. As the ecosystems within a landscape change due to natural or anthropogenic processes, they may go from being a carbon sink to a carbon source or vice versa. Satellite image analysis has been tested for timely and accurate measurement of spatially explicit land use change and is well suited for use in inventory and monitoring of terrestrial carbon. The coupling of Landsat Thematic Mapper (TM) data with a physiologically based forest productivity model (PnET-II) and historic climatic data provides an opportunity to enhance field plot-based forest inventory and monitoring methodologies. We use periodic forest inventory data from the U.S. Department of Agriculture (USDA) Forest Service’s Forest Inventory and Analysis (FIA) Program to obtain estimates of forest area and type and to generate estimates of carbon storage for evergreen, deciduous, and mixed-forest classes. The area information is used in an accuracy assessment of remotely sensed forest cover at the regional scale. The map display of modeled net primary production (NPP) shows a range of forest carbon storage potentials and their spatial relationship to other landscape features across the southern United States. This methodology addresses the potential for measuring and projecting forest carbon sequestration in the terrestrial biosphere of the southern United States.     

Comparison of organochlorine concentrations and patterns between free-ranging zooplankton and zooplankton sampled from seabirds' stomachs

To investigate the use of predators' stomach contents to measure the organochlorine load in free-ranging prey, the two zooplankton species Thysanoessa inermis (euphausiids) and Themisto libellula (amphipods) were collected simultaneously from the water column and from the seabird Brünnich's guillemot (Uria lomvia)'s stomach (from crop to proventriculus). The organochlorine compounds' concentrations and relative proportion of PCB-153 generally did not differ between the two sampling methods (least square mean of Sigma organochlorines=5.9 and 6.8 ng g(-1) wet weight for water column and stomach-sampled prey, respectively), indicating that the organochlorines in stomach-sampled prey were not yet affected by mechanical, chemical and bacterial degradation. Although the sample size is restricted, similar organochlorine concentrations and pattern in free-ranging and stomach-sampled prey may suggest that Brünnich's guillemots feed randomly on the zooplankton population rather than at more (or less) contaminated individuals. Alternatively or in addition, the similar concentrations and pattern suggest that the contaminant levels in Barents Sea zooplankton do not influence their behaviour to change the vulnerability to predation. In conclusion, the organochlorine concentrations and pattern in zooplankton collected from seabirds' stomach correspond with levels in free-ranging prey.     

Layer of organic pine forest soil on top of chlorophenol-contaminated mineral soil enhances contaminant degradation

Chlorophenols, like many other synthetic compounds, are persistent problem in industrial areas. These compounds are easily degraded in certain natural environments where the top soil is organic. Some studies suggest that mineral soil contaminated with organic compounds is rapidly remediated if it is mixed with organic soil. We hypothesized that organic soil with a high degradation capacity even on top of the contaminated mineral soil enhances degradation of recalcitrant chlorophenols in the mineral soil below. We first compared chlorophenol degradation in different soils by spiking pristine and pentachlorophenol-contaminated soils with 2,4,6-trichlorophenol in 10-L buckets. In other experiments, we covered contaminated mineral soil with organic pine forest soil. We also monitored in situ degradation on an old sawmill site where mineral soil was either left intact or covered with organic pine forest soil. 2,4,6-Trichlorophenol was rapidly degraded in organic pine forest soil, but the degradation was slower in other soils. If a thin layer of the pine forest humus was added on top of mineral sawmill soil, the original chlorophenol concentrations (high, ca. 70 μg g^?1, or moderate, ca. 20 μg g^?1) in sawmill soil decreased by >40 % in 24 days. No degradation was noticed if the mineral soil was kept bare or if the covering humus soil layer was sterilized beforehand. Our results suggest that covering mineral soil with an organic soil layer is an efficient way to remediate recalcitrant chlorophenol contamination in mineral soils. The results of the field experiment are promising.     

Toxicity of fenamiphos and its metabolites to the cladoceran Daphnia carinata: the influence of microbial degradation in natural waters

The acute toxicity of an organophosphorous pesticide, fenamiphos and its metabolites, fenamiphos sulfoxide, fenamiphos sulfone, fenamiphos phenol, fenamiphos sulfoxide phenol and fenamiphos sulfone phenol, to a cladoceran, Daphnia carinata was studied in both cladoceran culture medium and natural water collected from a local river. The toxicity followed the order: fenamiphos>fenamiphos sulfone>fenamiphos sulfoxide. The hydrolysis products of fenamiphos, F. sulfoxide (FSO) and F. sulfone (FSO(2)) (F. phenol, FSO phenol and FSO(2) phenol) were not toxic to D. carinata up to 500microgl(-1) water, suggesting hydrolysis reaction leads to detoxification. Also the toxicity was reduced in natural water compared to the cladoceran culture medium due to microbial mediated degradation of toxicants in the natural water. Fenamiphos and its metabolites were stable in both cladoceran water and filter-sterilised natural water while these compounds showed degradation in unfiltered natural water implicating the microbial role in degradation of these compounds. To our knowledge this is the first study on acute toxicity of fenamiphos metabolites to cladoceran and this study suggests that the organophosphate pesticides are highly toxic to fresh water invertebrates and therefore pollution with these compounds may adversely affect the natural ecosystems.     

Formation of volatile iodinated alkanes in soil: results from laboratory studies

Volatile iodinated organic compounds play an important role in the tropospheric photochemical system, but the current knowledge of the known sources and sinks of these alkyl iodides is still incomplete. This paper describes a new source of alkyl iodides from the pedosphere. Different organic-rich soils and humic acid were investigated for their release of volatile organoiodides. Six volatile organoiodides, iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane and 2-iodobutane were identified and their release rates were determined. We assume an abiotic reaction mechanism induced by the oxidation of organic matter by iron(III). The influence of iron(III), iodide and pH on the formation of alkyl iodides was investigated. Additionally, different organic substances regarded as monomeric constituents of humus were examined for the production of alkyl iodides. Two possible reaction pathways for the chemical formation of alkyl iodides are discussed. As humic acids and iron(III) are widespread in the terrestrial environment, and the concentration of iodide in soil is strongly enriched (compared to seawater), this soil source of naturally occurring organoiodides is suggested to contribute significantly to the input of iodine into the troposphere.     

Pattern and sources of naturally produced organohalogens in the marine environment: biogenic formation of organohalogens

The pattern of organohalogens found in the marine environment is complex and includes compounds, only assignable to natural (chloromethane) or anthropogenic (hexachlorobenzene, PCBs) sources as well as compounds of a mixed origin (trichloromethane, halogenated methyl phenyl ether).The chemistry of the formation of natural organohalogens is summarized. The focus is put on volatile compounds carrying the halogens Cl, Br, and I, respectively. Though marine natural organohalogens are quite numerous as defined components, they are mostly not produced as major compounds. The most relevant in terms of global annual production is chloromethane (methyl chloride). The global atmospheric mixing ratio requires an annual production of 3.5-5 million tons per year. The chemistry of the group of haloperoxidases is discussed. Incubation experiments reveal that a wide spectrum of unknown compounds is formed in side reactions by haloperoxidases in pathways not yet understood.     

Methodological aspects of a national population-based study of persistent organochlorine compounds in serum

Key methodological aspects are presented for a study of concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and organochlorine pesticides in the serum of a sample of the New Zealand population aged 15 years and older. The study took advantage of the sampling frame and sample collection and interview processes of the National Nutrition Study (NNS). An additional blood sample for this organochlorines study was collected by the NNS and questions added to the NNS questionnaire. Serum was obtained from the blood and, based on responses to questions in the questionnaire, samples with possible occupational exposure to organochlorines were excluded. Remaining samples providing at least 2 ml of serum were pooled within 80 strata defined according to geographic area, age group, sex and ethnicity. A minimum number of five individual serum samples was required for pooling within a stratum. Within strata with sufficient samples, two or three pooled samples were created for variance calculation. Eligible for inclusion in the study were 2497 individual serum samples. Sixty strata had sufficient serum samples for pooling and chemical analysis. This was the first study of organochlorine compounds with a national population-based sample. Two factors that made the study feasible deserve emphasis. First, being able to "piggy-back" on another study. Second, pooling of samples to reduce analytic expenses. It is hoped that the methods used in this study will form the basis for other studies investigating organochlorine concentrations in national populations.