Chemistry of soil solutions under different kinds of vegetation in the vicinity of a thermal power station

The influence of atmospheric deposition on the chemical characteristics of soil solutions in a small catchment area in NW Spain was studied. The soils, developed from slates, were sampled from seven sites supporting different forms of vegetation (deciduous and pine forest and heath). Soil solutions were extracted, by the column displacement method, from soil samples collected monthly from March 1992 until November 1993. The solutions were acidic with a low content of basic cations. The most common ions in all horizons were Cl(-) and Na(+), due to marine influence. In the surface horizons (0-10 cm), relatively high concentrations of SO(2-)4 (150-380 micromol litre(-1)) and Zn (approximately 2 micromol litre(-1)) were obtained, with good correlation between the two ions. These results, along with the prevalence of inorganic forms of Al (50-90% of total Al), were related to the effects of acidic deposition in the catchment area. The more rapid breakdown of litter in the soils under deciduous forest explains the greater ionic concentrations obtained in these solutions.     

Effects of acidic deposition on forest and aquatic ecosystems in New York State

Acidic deposition is comprised of sulfuric and nitric acids and ammonium derived from atmospheric emissions of sulfur dioxide, nitrogen oxides, and ammonia, respectively. Acidic deposition has altered soil through depletion of labile pools of nutrient cations (i.e. calcium, magnesium), accumulation of sulfur and nitrogen, and the mobilization of elevated concentrations of inorganic monomeric aluminum to soil solutions in acid-sensitive areas. Acidic deposition leaches essential calcium from needles of red spruce, making this species more susceptible to freezing injury. Mortality among sugar maples appears to result from deficiencies of nutrient cations, coupled with other stresses such as insect defoliation or drought. Acidic deposition has impaired surface water quality in the Adirondack and Catskill regions of New York by lowering pH levels, decreasing acid-neutralizing capacity, and increasing aluminum concentrations. Acidification has reduced the diversity and abundance of aquatic species in lakes and streams. There are also linkages between acidic deposition and fish mercury contamination and eutrophication of estuaries.     

Sulphur status in some Swedish podzols as influenced by acidic deposition and extractable organic carbon

To evaluate the changes in sulphur pools in response to acidic deposition, two studies were made-one in southwest Sweden where podzolic B horizons originally sampled in 1951 were resampled in 1989. At the Norrliden site, northern Sweden, sulphur pools in control plots were compared to plots that had been subjected to H(2)SO(4) application between 1971 and 1976. The results show that in southwest Sweden neither organic S nor extractable SO(4)(2-) increased significantly over the 38-year period, despite a decreasing pH and a high S deposition. At Norrliden, about 37% of the applied S was still remaining in the upper and central parts of the Bs horizon, most of which was inorganic sulphate. These contrasting results are explained by intrinsic differences in the soil organic carbon status between the sites-in southwest Sweden, organic carbon concentrations were high which inhibited SO(4)(2-) adsorption. Low organic carbon concentrations and high extractable Fe/Al concentrations promoted SO(4)(2-) adsorption and caused a low subsequent SO(4)(2-) desorption rate at the Norrliden site. The results suggest that sulphate adsorption may be an important mechanism which delays the response in soil chemistry to H(2)SO(4) deposition, provided that soil organic carbon concentrations are low. Organic S retention was not shown to be an important S retention mechanism in any of the sites studied.     

Speciation of zinc in contaminated soils

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100Lkg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.     

Phosphorus in waters from sewage sludge amended lysimeters

In surface waters, phosphorus (P) concentrations exceeding 0.05 mg liter(-1) may cause eutrophic conditions. This study was undertaken to measure total P concentrations in runoff and tile drainage waters from land receiving either inorganic fertilizer or anaerobically digested sewage sludge. Total P was measured in runoff and tile drainage waters during 2 years of sample collections from instrumented, large-scale lysimeters planted to corn (Zea mays L.). During the 3 years prior to monitoring P concentrations, six of the lysimeter plots had been amended with anaerobically digested sewage sludge which supplied 5033 kg P per ha. Additional sludge applications supplied 1058 and 1989 kg P per ha during the first and second years of monitoring operations, respectively. Another six lysimeters were annually treated with fertilizer which included P applications amounting to 112 kg ha(-1). For years 1 and 2, respectively, annual losses from lysimeters treated with sewage sludge were 4.27 and 0.35 kg P per ha in runoff and 0.91 from 0.91 and 0.51 kg Per P per ha in drainage waters. Parallel annual losses of P from lysimeters treated with superphosphate were 2.15 and 0.17 kg ha(-1) in runoff and 0.53 and 0.35 kg ha(-1) in tile drainage waters. Sludge applications did not significantly change absolute soil contents of organic P, but did decrease the per cent of total P present in organic forms. Sludge and soil, respectively, contained 21 and 36% of their total P contents in organic forms. In sludge and soil about 85 and 64% of their respective total inorganic P contents were associated with the Al and Fe fractions. Sludge applications significantly increased soil contents of P in the saloid (water-soluble plus P extracted with 1 N NH(4)Cl), Al, Fe and reductant soluble P fractions, but contents of Ca-bound P were not changed. Total P contents of the soil below a depth of 30 cm were not affected by sludge incorporated to a depth of about 15 cm by plowing.     

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH < 4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20 mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L⁻¹ using ⁷⁸Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H₂SO₄ and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments.     

The variations of aluminium species in mountainous forest soils and its implications to soil acidification

Aluminium (Al) speciation is a characteristic that can be used as a tool for describing the soil acidification process. The question that was answered is how tree species (beech vs spruce) and type of soil horizon affect Al speciation. Our hypotesis is that spruce and beech forest vegetation are able to modify the chemical characteristics of organic horizon, hence the content of Al species. Moreover, these characteristics are seasonally dependent. To answer these questions, a detailed chromatographic speciation of Al in forest soils under contrasting tree species was performed. The Jizera Mountains area (Czech Republic) was chosen as a representative mountainous soil ecosystem. A basic forestry survey was performed on the investigated area. Soil and precipitation samples (throughfall, stemflow) were collected under both beech and spruce stands at monthly intervals from April to November during the years 2008–2011. Total aluminium content and Al speciation, pH, and dissolved organic carbon were determined in aqueous soil extracts and in precipitation samples. We found that the most important factors affecting the chemistry of soils, hence content of the Al species, are soil horizons and vegetation cover. pH strongly affects the amount of Al species under both forests. Fermentation (F) and humified (H) organic horizons contain a higher content of water extractable Al and Al³⁺ compared to organo-mineral (A) and mineral horizons (B). With increasing soil profile depth, the amount of water extractable Al, Al³⁺ and moisture decreases. The prevailing water-extractable species of Al in all studied soils and profiles under both spruce and beech forests were organically bound monovalent Al species. Distinct seasonal variations in organic and mineral soil horizons were found under both spruce and beech forests. Maximum concentrations of water-extractable Al and Al³⁺ were determined in the summer, and the lowest in spring.     

Enhanced coagulation with polyaluminum chlorides: role of pH/alkalinity and speciation

Enhanced coagulation is considered to be among the best available techniques (BAT) for disinfection by-product (DBP) precursor removal in water treatment. Improving existing understanding requires further consideration of nuances of chemical speciation relative to source water chemistry. In this paper, the effect of alkalinity/pH and speciation on inorganic polymer flocculants, polyaluminum chlorides (PACls) for enhanced particle and natural organic matter (NOM) removal was investigated. Three kinds of well-characterized typical source waters in China with low, moderate, and high alkalinity were selected. Performance of coagulants is controlled not only by preformed species but also by those formed in situ. At neutral and basic pH values, PACls with higher basicity (ratio of OH(-)/Al), which have more stable preformed Alb (the rapid reacted species as in ferron assay), are more efficient for turbidity and NOM removal. At slightly acidic pH, PACls with lower basicity are more efficient since more Alb can be formed in situ. Optimal NOM removal was achieved at pH 5.5-6.5 for all PACls. Basicity, speciation, and dosage of coagulant should be optimized based on raw water alkalinity to enhance the removal efficiency of NOM.     

Cu and Zn mobilization in soil columns percolated by different irrigation solutions

We investigated the effects of different concentrations of nitrate and ammonium in irrigation water on the mobilization of Zn and Cu in repacked soil columns with a metal-polluted topsoil and unpolluted subsoils over two and a half years. Soil solution samples were collected by suction cups installed at vertical distances of a few centimeters and analyzed for dissolved organic carbon (DOC), Cu, and Zn (total and labile). During high N treatments the pH decreased and the presence of exchangeable cations resulted in Zn mobilization from the surface soil. The nitrogen input stimulated the biological activity, which affected both concentration and characteristics of DOC and consequently Cu speciation. Metal leaching through the boundary between the polluted topsoil and the unpolluted subsoils increased soil-bound and dissolved metals within the uppermost 2 cm in the subsoils. Our study shows that agricultural activities involving nitrogen fertilization can have a strong influence on metal leaching and speciation.     

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.     

Cumulative impact of 40 years of industrial sulfur emissions on a forest soil in west-central Alberta (Canada)

The impact of 40 years of sulfur (S) emissions from a sour gas processing plant in Alberta (Canada) on soil development, soil S pools, soil acidification, and stand nutrition at a pine (Pinus contorta x Pinus banksiana) ecosystem was assessed by comparing ecologically analogous areas subjected to different S deposition levels. Sulfur isotope ratios showed that most deposited S was derived from the sour gas processing plant. The soil subjected to the highest S deposition contained 25.9 kmol S ha(-1) (uppermost 60 cm) compared to 12.5 kmol S ha(-1) or less at the analogues receiving low S deposition. The increase in soil S pools was caused by accumulation of organic S in the forest floor and accumulation of inorganic sulfate in the mineral soil. High S inputs resulted in topsoil acidification, depletion of exchangeable soil Ca2+ and Mg2+ pools by 50%, podzolization, and deterioration of N nutrition of the pine trees.     

Controlling mechanisms of aluminium in soil solution--an evaluation of 180 podzolic forest soils.

To monitor the level of soil acidification in the county of V?rmland in the middle west of Sweden 180 podzolic forest soils were investigated. Soil solutions from four horizons were obtained by centrifugation and the soil was sampled for a determination of the exchangeable pool by extraction. The concentrations of inorganic Al and its fraction of the total Al in solution were greater in the south of the county (up to 50%). The factors influencing the total Al and free inorganic Al3+ in the soil solutions were evaluated. Saturation indices (SI) for five different mineral phases were calculated but none implied equilibrium conditions. The relationships between pAl3+ and pH (in the pH range 4-6.2) gave slopes of about 1, which indicated that ion exchange/complexation reactions may be important for determining the Al3+ concentration in the B and C horizons. In the E horizon solutions complexation with soluble organic acids seemed to be the major factor which influenced the Al3+ activity. The influence of organic matter on Al solubility was supported by partial least square (PLS) regressions.     

Response of drinking-water reservoir ecosystems to decreased acidic atmospheric deposition in SE Germany: trends of chemical reversal

This study evaluates chemical trends of seven acidified reservoirs and 22 tributaries in the Erzgebirge from 1993 to 2003. About 85% of these waters showed significantly (p < 0.05) declining concentrations of protons (-69%), nitrate (-41%), sulfate (-27%), and reactive aluminum (-50% on average). This reversal is attributed to the intense reduction of industrial SO2 and NOx emissions from formerly high levels, which declined by 99% and 82% in the German-Czech border region between 1993 and 1999. The deposition rates of protons and sulfur decreased by 70-90%. Since 1993, the dry deposition of total inorganic nitrogen diminished to a minor degree, but the wet deposition remained unchanged. The surface waters reflect a substantial decrease in Al exchange processes, a release of sulfur previously stored in soils, and an uptake of nitrate by forest vegetation. The latter effect may be supported by soil protection liming which contributed to the chemical reversal in almost 20% of the study waters.     

Arsenic species and leachability in the fronds of the hyperaccumulator Chinese brake (Pteris vittata L.)

Arsenic speciation is important not only for understanding the mechanisms of arsenic accumulation and detoxification by hyperaccumulators, but also for designing disposal options of arsenic-rich biomass. The primary objective of this research was to understand the speciation and leachability of arsenic in the fronds of Chinese brake (Pteris vittata L.), an arsenic hyperaccumulator, with an emphasis on the implications for arsenic-rich biomass disposal. Chinese brake was grown for 18 weeks in a soil spiked with 50 mg As kg(-1) as arsenate (AsO4(3-)), arsenite (AsO3(3-)), dimethylarsinic acid (DMA), or methylarsonic acid (MMA). Plant samples were extracted with methanol/water (1:1) and arsenic speciation was performed using high performance liquid chromatography coupled with atomic fluorescence spectrometry. The impacts of air-drying on arsenic species and leachability in the fronds were examined in the laboratory. After 18 weeks, water-soluble arsenic in soil was mainly present as arsenate with little detectable organic species or arsenite regardless of arsenic species added to the soil. However, arsenic in the fronds was primarily present as inorganic arsenite with an average of 94%. Arsenite re-oxidation occurred in the old fronds and the excised dried tissues. Arsenic species in the fronds were slightly influenced by arsenic forms added to the soil. Air-drying of the fronds resulted in leaching of substantial amounts of arsenic. These findings can be of significance when looking at disposal options of arsenic-rich biomass from the point of view of secondary contamination.     

The dynamics of dissolved nitrogen in a blanket peat dominated catchment

Precipitation, soil solution and drainage water were collected from a blanket peat catchment at Moor House National Nature Reserve in the Northern Pennine Uplands, UK, an area of moderately high N deposition. Two tributaries of the main stream were also sampled. Between 1993 and 1995 samples were analysed for NH4+ and NO3- and for part of the period for organic N. Inputs of N in precipitation exceeded outputs in stream water. Organic N represented a small proportion of N inputs while inputs of inorganic N averaged 10.2 kg ha(-1) a(-1). Soil solution from 10 cm depth in the peat was dominated by organic N whereas at 50 cm NH4+ slightly exceeded organic N. NO3- was rarely detected at either depth except during a period of exceptionally warm and dry weather in 1995. Output fluxes in stream water of organic N (5.7 to 6.5 kg ha(-1) a(-1)) were much greater than those of inorganic N (0.6 to 2.2 kg ha(-1) a(-1)). Inorganic N in streams was predominantly NO3- except in the smallest stream which had the largest concentrations of NH4+. This suggests that N transformations, particularly nitrification, may be taking place in the mineral soils adjacent to the streams or within the stream channel of the larger catchment.     

Effect of biosolid incorporation on arsenic distribution in Mollisol soils in central Chile

The effect of biosolid incorporation on arsenic distribution in Mollisol soils in central Chile was studied. Two soils were sequentially extracted for arsenic with a five-step method that accounts for the following arsenic forms: non-specifically adsorbed (F1), specifically adsorbed (F2), amorphous and poorly crystallized Fe and Al oxides (F3), well-crystallized Fe and Al oxides (F4) and residual (F5). The arsenic residual fraction was predominant in Pintué soil, whereas in Graneros soil, arsenic was mostly associated to amorphous Fe and Al oxides. Graneros soil exhibited a higher As(V) adsorbing capacity than Pintué soil, which relates to the higher clay and iron and aluminum oxides contents, confirming that these components participation is essential for the adsorption of this metalloid. Biosolid application at a rate of 100Mg ha(-1) caused an increase in arsenic bound to amorphous Fe and Al oxides and in the residual fraction, in Pintué soil. When Pintué soil was spiked with arsenic, aged for two months, and treated with biosolid (100Mg ha(-1)), the content of arsenic in the most labile fractions decreased, thus showing a favorable effect in its application to soils with few specific sites for arsenic adsorption. Arsenic speciation was carried out in the first two fractions of the sequential extraction procedure. As(V) was the main form in both fractions. Biosolid incorporation at a rate of 100Mg ha(-1) caused a significant increase in organic arsenic forms.     

Soil solutions and surface water analysis in two contrasted watersheds impacted by acid deposition, Vosges mountains, N.E. France: interpretation in terms of Al impact and nutrient imbalance

Two acid watersheds in the Vosges mountains (N.E. France), one with a podzol, the other with an acid brown soil, were monitored by analysing soil solutions and two related springs for total chemistry and Al speciation. High concentrations of inorganic Al did not occur in the podzol upper horizons but were evident in the corresponding spring, together with low concentrations of Ca. In the acid brown soil area, high concentrations of inorganic Al occurred in the leaching water draining the upper soil horizons, but not in the undrained water nor in the spring, the latter exhibiting rather high Ca content. In both watersheds, needle yellowing in conifers could be observed and might be ascribed to Mg deficiency rather than to Al toxicity.     

Deposition of Mn from Automotive Combustion of Methylcyclopentadienyl Manganese Tricarbonyl beside the Major Highways in the Greater Toronto Area,Canada

ABSTRACT

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used in Canada since 1976 as an antiknock agent in gasoline, completely replacing Pb in 1990. An early study of much higher Mn concentrations in gasoline showed that the combustion of MMT leads to the formation of inorganic manganese oxides, especially Mn₃O₄. Recent emission testing by Lawrence Livermore National Laboratory for Ethyl Corp. has shown that Mn is primarily emitted as a phosphate or sulfate along with minor amounts of oxides. The main objective of this research was to analyze the deposition of Mn from MMT to the terrestrial environment beside the major highways in the greater Toronto area (GTA), Canada. The results were compared with Pb and other trace elements such as Al, Ca, Fe, Mg, Cu, Zn, Na, and the Cl^- ion (water extractable) to study the behavior of Mn in soil. The study area was located near major Toronto highways 401 (urban) and 400 (rural), at 43° 67′ N and 79° 37′ W (latitude and longitude) (278,560 and 47,835 cars/day), respectively. Surface soil samples (0–5 cm depth) were collected at distances up to 40 m from the roadside. Parameters evaluated included total and available Mn and other trace elements, particle size, pH, organic content, and cation exchange capacity.     

Mobilization of soil organic matter by complexing agents and implications for polycyclic aromatic hydrocarbon desorption

Complexing agents are frequently used in treatment technologies to remediate soils, sediments and wastes contaminated with toxic metals. The present study reports results that indicate that the rate and extent of soil organic matter (SOM) as represented by dissolved natural organic carbon (DNOC) and polycyclic aromatic hydrocarbon (PAH) desorption from a contaminated soil from a manufactured gas plant (MGP) site can be significantly enhanced with the aid of complexing agents. Desorption of DNOC and PAH compounds was pH dependent, with minimal release occurring at pH 2-3 and maximal release at pH 7-8. At pH-6, chelate solutions were shown to dissolve large amounts of humic substances from the soil compared to controls. The complexing agents mobilized polyvalent metal ions, particularly Fe and Al from the soil. Metal ion chelation may disrupt humic (metal ion)-mineral linkages, resulting in mobilization of SOM and accompanying PAH molecules into the aqueous phase; and/or reduce the degree of cross-linking in the soil organic matter phase, which could accelerate PAH diffusion.     

Responses of microbial populations in the rhizosphere to deposition of simulated acidic rain onto foliage and/or soil

Air pollutants or some chemicals applied to plant foliage can alter the ecology of the rhizosphere. Experiments were conducted to distinguish among possible foliage-mediated versus soil- or root-mediated effects of acid deposition on microorganism in the rhizosphere. Seedlings of a sorghum x sudangrass hybrid in pots of non-sterile soil-sand mix in a greenhouse were exposed to simulated rain solution adjusted with H2SO4 + HNO3 to pH 4.9, 4.2, 3.5 or 2.8. Solutions were applied as simulated rain to foliage and soil, foliage only (soil covered by plastic, and deionized water applied directly to the soil), or soil only (solution applied directly to the soil). Solutions were applied on 16 days during a 6-week period (1.5 cm deposition in 1 h per application). Plant shoot and root dry weights and population densities of selected types of bacteria, filamentous actinomycetes and fungi in the rhizosphere were quantified after exposures were completed. Deposition of simulated acidic rain onto foliage alone had no effect on plant biomass or microbial population densities in the rhizosphere (colony-forming units per gram of rhizosphere soil). However, plant growth was stimulated and all microbial populations in the rhizosphere increased 3- to 8-fold with increased solution acidity (relative to pH 4.9 solution) when solution penetrated the soil. Statistical analyses indicated that the acid dose-population response relationships for soil-only and foliage-and-soil applications were not different. Thus, no foliage-mediated effect of simulated acidic rain on rhizosphere ecology was detected.