Spatial patterns of organic chlorine and chloride in Swedish forest soil

The concentration of organic carbon, organic chlorine and chloride was determined in Swedish forest soil in the southern part of Sweden and the spatial distribution of the variables were studied. The concentration of organically bound chlorine was positively correlated to the organic carbon content, which is in line with previous studies. However, the spatial distribution patterns strongly indicate that some other variable adds structure to the spatial distribution of organic chlorine. The distribution patterns for chloride strongly resembled the distribution of organic chlorine. The spatial distribution of chloride in soil depends on the deposition pattern which in turn depends on prevailing wind-direction, amount of precipitation and the distance from the sea. This suggests that the occurrence of organic chlorine in soil is influenced by the deposition of chloride or some variable that co-varies with chloride. Two clearly confined strata were found in the area: the concentrations of organic chlorine and chloride in the western area were significantly higher than in the eastern area. No such difference among the two areas was seen regarding the carbon content.     

Leaching of mercury from peat soil

The factors influencing the sorption and leaching of mercury in peat soil were studied using small additions of labelled mercury in peat lysimeters. Additions of chloride, fertilizer or sterilant did not affect the leaching of mercury. Complete drying of the peat improved the leaching of mercury probably because of changes in the physical properties of the peat soil.     

Flow rates of ions in waters percolating through a model ecosystem with forest trees

From 1983-88 the long-term effects of low level exposure with O(3), SO(2) and simulated acid rain on mineral cycling in model ecosystems with spruce, fir and beech seedlings were investigated. Systems consisting of open-top chambers built above lysimeters were protected against the intrusion of ambient rain and dust. As part of the investigations on mineral cycling the fluxes of elements with water input and output of the canopy and soil compartments are presented. During the 5 year duration of the experiment, pronounced effects on canopy deposition and cation leaching were observed. Most noticeable were throughfall enrichment with sulfate through dry deposition of SO(2) as influenced by duration of needlewetting and factors promoting SO(2) oxidation. Depending on sulfur deposition, leaching of calcium, magnesium, manganese, zinc and ammonium from canopies was elevated, in total leading to enhanced soil input of acid. After 15 months, the water percolating the soils in the lysimeters of these treatments was acidified, with elevated flowrates of sulfate, manganese, calcium and magnesium. The results on canopy/soil leaching are compared to those from old conifer stands in the field.     

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.     

Changes in soil organic carbon storage under grassland as evidenced by changes in sulphur input-output budgets

Information about temporal changes in soil organic carbon (C) pools may be obtained indirectly from changes in input-output budgets of organically combined nutrients such as sulphur (S). Sulphur budgets were therefore evaluated for Northern Ireland (NI) for the period 1940-1990, inclusive. These budgets indicated that the land or soil had acted first as a sink but then as a source for S, and that reserves of soil S built up between 1940 and 1965 were totally depleted by the mid-1980s. Pooled data from six long-term soil-monitoring sites on undisturbed grassland suggested that negative S budgets from the late-1970s onwards had been due to the net mineralization of soil organic matter and thus were indicative of net losses of organic C from surface soil horizons. There was some evidence that the decline in rainfall and fertiliser S inputs from the mid-1960s may have precipitated the breakdown of soil organic matter.     

Modelling long-term cation supply in acidified forest stands

A dynamic soil chemistry model was used to explain the observed decrease in soil base saturation between 1949 and 1984 at three stands in southern Sweden. The results show that acid deposition has caused soil acidification. The model, SAFE (Soil Acidification in Forest Ecosystems), includes the fundamental physical processes such as leaching and accumulation, and chemical processes such as cation exchange, mineral weathering, nutrient uptake and solute equilibrium reactions. The sources and sinks of base cations in the soil system were quantified, showing that weathering, deposition of base cations and depletion of exchangeable base cations supply cations to the soil solution in similar amounts in the upper 1 m during the acidification phase. This demonstrates that budget studies alone cannot be used to distinguish between long-term capacity to resist acidification, represented by weathering, from short-term buffering caused by cation exchange.     

Stabilization of Pb- and Cu-contaminated soil using coal fly ash and peat

The stabilization of metal contaminated soil is being tested as an alternative remediation method to landfilling. An evaluation of the changes in Cu and Pb mobility and bioavailability in soil induced by the addition of coal fly ash and natural organic matter (peat) revealed that the amount of leached Cu decreased by 98.2% and Pb by 99.9%, as assessed by a batch test. Metal leaching from the treated soil was lower by two orders of magnitude compared to the untreated soil in the field lysimeters. A possible formation of mineral Cu- and Pb-bearing phases and active surface with oxides were identified by chemical equilibrium calculations. Low metal leaching during a two-year observation period, increased seed germination rate, reduced metal accumulation in plant shoots, and decreased toxicity to plants and bacteria, thereby demonstrating this stabilization method to be a promising technique for in situ remediation of Cu and Pb contaminated soil.     

The flux of chloroform and tetrachloromethane along an elevational gradient of a coastal salt marsh, East China

The fluxes of trichloromethane (CHCl(3), CM) and tetrachloromethane (CCl(4), TCM) were seasonally measured using static flux chambers over an annual cycle in a coastal salt marsh, East China. The salt marsh presented as a large sink for both the compounds in the growing season (from April to October), but it was a minor source for the gas species in the non-growing season. Generally, the cordgrass marsh acted as a sink of CM and TCM. The net consumption of CM and TCM observed in the study marsh may result from the high ambient atmospheric concentrations and enriched soil organic matter that result in anoxic sediments. Higher plants were suggested to be an important sink for CM and TCM in the growing season, but a net source in the non-growing season. However, the mechanism responsible for the plant removal process is not clear.     

Removal of methyl chloroform in a coastal salt marsh of eastern China

The atmospheric burden of methyl chloroform (CH(3)CCl(3)) is still considerable due to its long atmospheric lifetime, although CH(3)CCl(3) emissions have declined considerably since it was included into the Montreal Protocol. Moreover, CH(3)CCl(3) emissions are used to estimate hydroxyl radical (OH) levels, trends, and hemispheric distributions, and thus the mass balance of the trace gas in the atmosphere is critical for characterizing OH concentrations. Salt marshes may be a potential sink for CH(3)CCl(3) due to its anoxic environment and abundant organic matter in sediments. In this study, seasonal dynamics of CH(3)CCl(3) fluxes were measured using static flux chambers from April 2004 to January 2005, along an elevational gradient of a coastal salt marsh in eastern China. To estimate the contribution of higher plants to the gas flux, plant aboveground biomass was experimentally harvested and the flux difference between the treatment and the intact was examined. In addition, the flux was analyzed in relation to soil and weather conditions. Along the elevational gradient, the salt marsh generally acted as a net sink of CH(3)CCl(3) in the growing season (from April to October). The flux of CH(3)CCl(3) ranged between -3.38 and -32.03 nmol m(-2)d(-1) (positive for emission and negative for consumption), and the maximum negative rate occurred at the cordgrass marsh. However, the measurements made during inundation indicated that the mudflat was a net source of CH(3)CCl(3). In the non-growing season (from November to March), the vegetated marsh was a minor source of CH(3)CCl(3) when soil was frozen, the emission rate ranging from 3.43 to 7.77 nmol m(-2)d(-1). However, the mudflat was a minor sink of CH(3)CCl(3) whether it was frozen or not in the non-growing season. Overall, the coastal salt marsh in eastern China was a large sink for the gas, because the magnitude of consumption rate was lager than that of emission, and because the duration of the growing season was longer than that of the non-growing season. Plant aboveground biomass had a great effect on the flux. Comparative analysis showed that the direction and magnitude of the effect of higher plants on the flux of CH(3)CCl(3) depended on timing of sampling vegetation type. In the growing season the plant biomass decreased the gas flux and acted as a large sink of the gas, whereas it presented as a minor source in the non-growing season. However, the mechanism underlying plant uptake process is not clear. The CH(3)CCl(3) flux was positively related to the dissolved salt concentration and organic matter content in soil, as well as light intensity, but it was negatively related to soil temperature, sulfate concentrations, and initial ambient atmospheric concentrations of CH(3)CCl(3). Our observations have important implications for estimation of the tropospheric lifetime of CH(3)CCl(3) and global OH concentration from the global budget concentration of CH(3)CCl(3).     

Leaching of pesticides through normal-tillage and low-tillage soil--a lysimeter study. II. Glyphosate

Glyphosate is a widely used non-selective herbicide. Leaching of glyphosate (N-(phosphonomethyl)glycine) and/or its metabolite AMPA (aminomethylphosphonic acid) was studied in four lysimeters, two of them being replicates from a low-tillage field (lysimeter 3 and 4), the other two being replicates from a normal tillage field (lysimeter 5 and 6). In both cases the soil was a sandy loam soil with 13-14% clay. The lysimeters had a surface area of 0.5 m2 and a depth of 110 cm. Lysimeter 3 and 4 were sprayed with a mixture of 14C-labelled glyphosate and unlabelled glyphosate, while lysimeter 5 and 6 were sprayed with unlabelled glyphosate. The spraying took place September 18, 1997. The total amount of glyphosate sprayed onto each lysimeter was 40 mg, corresponding to 0.8 kg active ingredient per ha. The lysimeters were installed in an outdoor system in Research Centre Flakkebjerg and were thus exposed to normal climatic conditions of the area. A mean of 260 l drainage water were collected from lysimeter 3 and 4 and a mean of 375 litres from lysimeter 5 and 6. The mean yearly concentration of leached glyphosate and/or AMPA was significantly below 0.1 microg/l from both sets of lysimeters, and thus no significant difference between the two lysimeter sets was shown. However, in both sets of lysimeters several single findings at concentrations above 0.1 microg/l was seen, which might be due to the leaching of particle-bound compounds. A significant difference between the soil residual concencentrations of AMPA was seen, the higher concentration was found in the set of lysimeter where low-tillage had been practiced and where Round Up had been used several times in the years before sampling of the lysimeter soil.     

Soil-Atmosphere exchange of radiatively and chemically active gases

Exchanges between the soils and the atmosphere may control or significantly affect the global budgets of many environmentally important trace gases, both natural and man-made. Flux measurements, taken in several ecosystems, show that soils are a substantial source of chloroform (8 ± 4 μg/m²/d) and a sink for methyl chloride (-10 _-3 ⁺⁶ μg/m²/d). The known sources and sinks of these gases are insufficient to explain the observed concentrations. Our findings will help to balance the global budget of chloroform but may put the budget of methyl chloride further out of balance. We also found, consistent with previous research, that soils are a substantial source of nitrous oxide and carbon monoxide and take up hydrogen and methane. The uptake of man-made chlorocarbons was observed, but the rates are small. Observed fluxes of non-methane hydrocarbons showed few patterns except that soils may be a source of ethane and butane.     

Formation and transport of PCDD/Fs in the packed bed of soil containing organic chloride during a thermal remediation process

The authors previously proposed the concept of a new thermal remediation process for particulate/powder materials contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and experimentally verified its validity on the basis of process efficiency. However, contaminees such as soils and fly ashes from waste incinerators often contain a considerable amount of other chlorides, which may act as a main source of chlorine in the formation of PCDD/Fs via thermal processes. The present study aims to examine the formation and transport of PCDD/Fs in the packed bed of soil containing a chloride during the process. Polyvinyl chloride (PVC) polymer was mixed with soil sample as an organic chloride model. A laboratory-scale apparatus was employed as a process simulator. Further, a technique to quench the process was applied to observe the concentration distribution of PCDD/Fs in the solid bed in the vertical direction. The result shows that the PCDFs tend to form dominantly in the high temperature (calcination and/or combustion) zone and are successively trapped in the low temperature (wet) zone. Especially, TeCDF is the most dominant homologue contained in the wet zone and outlet gas. Although PCDD/Fs are once trapped at the wet zone, the concentration of the remediated materials gives fairly low value (1.9 pg/g-dry, 0.04 pg-TEQ/g-dry). It signifies that organic chlorides mingled in the solid contaminee not affect the removal efficiency of PCDD/Fs in the process. Nevertheless, attention should be paid to the potential emission of PCDD/Fs in the outlet gas due to the presence of organic chloride in the soil.     

Nitrogen deposition increases the acquisition of phosphorus and potassium by heather Calluna vulgaris

Increased plant productivity due to nitrogen pollution increases the strength of the global carbon sink, but is implicated in plant diversity loss. However, modelling and experimental studies have suggested that these effects are constrained by availability of other nutrients. In a survey of element concentrations in Calluna vulgaris across an N deposition gradient in the UK, shoot concentrations of N and more surprisingly phosphorus and potassium were positively correlated with N deposition; tissue N/P ratio even decreased with N deposition. Elevated P and K concentrations possibly resulted from improved acquisition due to additional enzyme production or mycorrhizal activity. Heather occurs on organic soils where nutrient limitations are likely due to availability constraints rather than small stocks. However, if this effect extends to other plant and soil types, effects of N deposition on C sinks and plant competition may not be as constrained by availability of other nutrients as previously proposed.     

The effect of inorganic and organic chlorine on formation of highly chlorinated organic compounds during incineration: Laboratory pilot study

Aliphatic liquid as a basic fuel was incinerated in a laboratory scale pilot plant. Inorganic chlorine and organic chlorine mixed with basic fuel were used as additive chemicals. Sodium chloride (NaCl) and tetrachloroethylene (C₂Cl₄) were used as the sources of inorganic and organic chlorine. Combustion parameters were adjusted for optimum combustion and, consequently, the amount of particles in flue gases was low. The concentrations of chlorine in flue gases were high enough for possible formation reactions of organic chlorinated compounds in all of the chlorine input tests. An increase in chlorine input did not significantly increase the amounts of highly chlorinated organic compounds, like PCDD/Fs. The main result was that chlorophenol concentrations increased in parallel with organic chlorine input. Comparing organic chlorine to inorganic chlorine tests showed that more highly substituted PCDD/F congeners were formed when organic chlorine was the additive chlorine source. The formation of highly chlorinated organic compounds such as PCDD/Fs requires not only chlorine and aliphatic fuel to be formed, but some catalysts are also needed.     

CO2 deficit in temperate forest soils receiving high atmospheric N-deposition

Evidence is provided for an internal CO2 sink in forest soils, that may have a potential impact on the global CO2-budget. Lowered CO2 fraction in the soil atmosphere, and thus lowered CO2 release to the aboveground atmosphere, is indicated in high N-deposition areas. Also at forest edges, especially of spruce forest, where additional N-deposition has occurred, the soil CO2 is lowered, and the gradient increases into the closed forest. Over the last three decades the capacity of the forest soil to maintain the internal sink process has been limited to a cumulative supply of approximately 1000 and 1500 kg N ha(-1). Beyond this limit the internal soil CO2 sink becomes an additional CO2 source, together with nitrogen leaching. This stage of "nitrogen saturation" is still uncommon in closed forests in southern Scandinavia, however, it occurs in exposed forest edges which receive high atmospheric N-deposition. The soil CO2 gradient, which originally increases from the edge towards the closed forest, becomes reversed.     

Distribution of Al-, Fe- and Mn-pools and their correlation in soils from two acid deposition small catchments in Hunan, China

Distribution of Al-, Fe- and Mn-pools was investigated in five forest soil profiles (consisting of four horizons) in each of two Hunan catchments (BLT and LKS) where acid deposition has been considered critical. Al- and Fe-pools were higher in BLT than those in LKS, but Mn-pools much lower in BLT. Mn-pools vary from topsoils to bottom soils, but there are different trends for different Mn speciation. Al- and Fe-pools, except amorphous Fe_ox, were positively correlated to contents of soil organic matter (OM) showed by the loss on ignition in the two catchments. Accumulation of Al- and Fe-pools may occur in the area where soil organic matter was enriched (e.g. in top soil and rhizosphere soil). However, no direct correlation is observed between Mn and OM. Acidic atmospheric deposition may affect transforming among speciations of Al-, Fe- and Mn-pools and leaching of soil Al, Fe and Mn through formation of soluble organo-metal dissolved Al which was potentially toxic, increased. There were significant correlations between Al-pools complexes or change of oxidation–reduction conditions. Mn_ex (exchangeable Mn) and Mn_ox (amorphous and organic Mn) were highly linearly correlation with soil pH values at LKS but at BLT. Under acid deposition, the availability of the nutrient Fe increased with the amount of dissolved Al, which was potentially toxic, in the two catchments. There are no significant correlations between Al_ex (exchangeable Al) and Mn_ex, Fe_ex (exchangeable Fe) and Mn_ex in this work, indicating potentially toxic Mn increase seldom accompanying with Al increase in the two catchments.     

Effects of sewage sludge amendments on pesticide sorption and leaching through undisturbed Mediterranean soils

The Gharb region in Morocco is an important agricultural zone where soils receive pesticide treatments and organic amendments to increase yields. The groundwater aquifer in the Gharb region is relatively shallow and thus vulnerable. The objective of this work was to study the influence of organic amendments on diuron, cyhalofop-butyl and procymidone leaching through undisturbed soil columns. Two soils were sampled from the Gharb region, a Dehs (sandy soil) and a R’mel (loamy clay soil). Following elution (124.5 mm), the amount of pesticide residues in the leachates of the sandy soil (0.06–0.21 %) was lower than in those of the loamy clay soil (0.20–0.36 %), which was probably due to preferential flow through the loamy clay soil. The amount of procymidone leached through the amended soil columns was greater than the control for the sandy soil only. The organic amendments did not significantly influence diuron and cyhalofop-butyl leaching in either of the soils. The application of organic amendments affected the amounts of dissolved organic matter (DOM) eluted and thus pesticide leaching as a function of soil-type. Nevertheless, in some case, the formation of pesticide-DOM complexes appeared to promote pesticide leaching, thus increasing groundwater contamination risks.     

Effects of sewage sludge amendments on pesticide sorption and leaching through undisturbed Mediterranean soils

The Gharb region in Morocco is an important agricultural zone where soils receive pesticide treatments and organic amendments to increase yields. The groundwater aquifer in the Gharb region is relatively shallow and thus vulnerable. The objective of this work was to study the influence of organic amendments on diuron, cyhalofop-butyl and procymidone leaching through undisturbed soil columns. Two soils were sampled from the Gharb region, a Dehs (sandy soil) and a R'mel (loamy clay soil). Following elution (124.5 mm), the amount of pesticide residues in the leachates of the sandy soil (0.06-0.21 %) was lower than in those of the loamy clay soil (0.20-0.36 %), which was probably due to preferential flow through the loamy clay soil. The amount of procymidone leached through the amended soil columns was greater than the control for the sandy soil only. The organic amendments did not significantly influence diuron and cyhalofop-butyl leaching in either of the soils. The application of organic amendments affected the amounts of dissolved organic matter (DOM) eluted and thus pesticide leaching as a function of soil-type. Nevertheless, in some case, the formation of pesticide-DOM complexes appeared to promote pesticide leaching, thus increasing groundwater contamination risks.     

Chernoff-Flury faces: a statistical means for representing multivariate response parameters of air pollution induced injury on plants

To evaluate the effects of dry and wet deposition on forest trees (Picea abies [L.] Karst.), the LIS-Essen is operating an Open-Top Chamber Field Station within an area where novel forest decline has been prevalent since 1982. Chambers are ventilated with either ambient or charcoal-filtered air and receive either natural or artificial rain, the latter being prepared by natural rain and distilled water in ratio 1:10. Besides deposition data, acquired above and below the tree crowns as well as via lysimeters of soil percolates, various parameters describing vitality of trees are measured. To obtain a persuading representation of total parameters and their interdependencies, a multivariate graphical cluster analysis has been performed by use of Chernoff-Flury faces. Interdependencies of vitality parameters are more easily recognizable in this multivariate picture than in usually applied binary correlation diagrams.     

A reactive transport model for mercury fate in soil—application to different anthropogenic pollution sources

Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg²⁺ to Hg⁰ was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg²⁺ with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg²⁺ sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of contaminated sites are discussed.