Comparison of various methods for the determination of inorganic species in airborne atmospheric particulates

The performance of various filters used for determining inorganic species (heavy metals, light metals, anions and ammonium ion) in airborne particulates was comparatively assessed. Filters used in the determination of Ca²⁺, Mg²⁺, Na⁺, K⁺, Fe³⁺, Zn²⁺, Pb²⁺, Cr³⁺, Ni²⁺, V (V), Mn²⁺ and Cd²⁺ were attacked by acid extraction (glass microfibre filters, GF/A), acid extraction and microwave oven digestion (quartz filters, QM-A), and muffle furnace calcination and microwave oven digestion (Whatman-41 cellulose filters, W-41). The behaviour of the different filters tested towards aqueous extraction for the determination of anions (Cl^?, NO ₃ ^? , SO ₄ ^? , ammonium ion and light metals (Ca²⁺, Mg²⁺, Na⁺ and K⁺) was also studied and the results obtained for the light metals were compared with those provided by acid attack. All metals except vanadium were determined by ICP-AES; cadmium, lead and vanadium were analysed for by GFAAS; anions were quantified by ion chromatography (SO ₄ ^? was also measured by ICP-AES); and ammonium ion was determined by the Indophenol Blue method.     

Adsorption features of Cu(II), Pb(II), and Zn(II) by an ordinary chernozem from nitrate,chloride, acetate,and sulfate solutions

The effect of Cl^?,SO ₄ ^2? , CH₃COO^?, and NO ₃ ^? anions on the adsorption of copper, lead, and zinc by an ordinary chernozem has been studied. The effect of the anions on the adsorption of Cu²⁺, Pb²⁺, Zn²⁺ ions is significant but uncertain. It has been shown that the attendant anions affect the shape of the adsorption isotherms, which are described by the Langmuir, Freundlich, or Henri equations. The constants of the adsorption from a nitrate solution calculated from the Langmuir equation (K _L) decrease in the following order: Cu²⁺ > Pb²⁺ >> Zn²⁺. The values of the maximum adsorption (C _max) decrease in the following order: Cu²⁺ ≥ Zn²⁺ > Pb²⁺ for acetate solutions and in the series Pb²⁺ > Zn²⁺ ≥ Cu²⁺ for nitrate solutions. The values of the Henry constants (K _H) calculated for the adsorption of the same cations from chloride solutions decrease in the same order as the values of K _L. The CH₃COO^? anion has the highest effect on the constant values. The NO ₃ ^? and Cl^? anions “switch their places” depending on the attendant cation, but their effect is always lower than that of the acetate anion. The values of C _max for copper and zinc are most affected by the CH₃COO^? anion, and the adsorption of zinc is most affected by the Cl^? and NO ₃ ^? anions. The assessment of the mobility of the adsorbed cations from the extraction with ammonium acetate (pH 4.8) has shown that the content of the desorbed metals is always lower than the content of the adsorbed cations and varies from 0.025 to 83%. According to their mobility, the adsorbed metals form the following order: Zn²⁺ > Pb²⁺ > Cu²⁺. The effect of the attendant anions on the extractability of the adsorbed cations decreases in the following order: chlorides > sulfates > acetates > nitrates.     

Loading of VO2+ and Cu2+ to partially oxidized charcoal fines rejected from Brazilian metallurgical industry

Purpose

Charcoal is utilized in Brazil for the metallurgical industry. Small size pieces, called charcoal fines, are rejected and sometimes are used to produce energy by burning. This charcoal can be used as soil conditioner to improve retention of metal ions in soil. However, changing the charcoal's surface chemistry via oxidation may increase retention of metal ions.

Materials and methods

Two kinds of oxidants were employed, nitric acid and selenium dioxide/hydrogen peroxide. Vanadyl ion (VO²⁺) and copper ion (Cu²⁺) were utilized as probe to study the metal ion complexation by the partially oxidized charcoal obtained. FTIR and EPR spectroscopy were used to characterize the materials.

Results and discussion

Oxidation with nitric acid increased nitrogen content, while oxidation with SeO₂/H₂O₂ elevated carbon content of treated charcoals. Organic free radicals (OFRs) with the unpaired electron in p orbitals of aromatic structures were confirmed by the EPR g-factors that ranged from 2.0038 to 2.0031. The oxidation with selenium dioxide/hydrogen peroxide formed charcoal with largest quantity of OFR. Loading charcoal with VO²⁺ and Cu²⁺ resulted in formation of complexes were oxygen acted as coordination atom. The formed complexes were of axial symmetry. The configurations around the Cu²⁺ ions were: CUNCu²⁺ complex (more stable square planar symmetry) and CFNCu²⁺ complex (less stable distorted tetrahedral configuration). Both complexes had oxygen as coordinating atoms. CFNVO²⁺ and CFSeVO²⁺ complexes presented complexation sites of axial symmetry, C_4v, with oxygen as coordinating atoms.

Conclusions

The oxidative treatment of charcoal with SeO₂/H₂O₂ is more appropriate to produce soil organic conditioner for complexation of metal ions.     

Biotite weathering by <Emphasis Type="Italic">Aspergillus niger</Emphasis> and its potential utilisation

Purpose

Biotite, as a type of associated mineral, is normally applied as a filling material for buildings, or is discarded as tailings. However, as a potassium-bearing phyllosilicate mineral, biotite can be easily weathered by fungi, which leads to its internal potassium being released for agricultural production (1), and the mineral residues being weathered by the fungus may be applied for adsorption of heavy metal ions (2).

Materials and methods

This work investigates the weathering of biotite by Aspergillus niger through the analysis of the differences in ion dissolution from biotite, producing of organic acids, the change of mineral morphology and composition by inductively coupled plasma optical emission spectrometry (ICP-OES), high-performance liquid chromatography (HPLC), scanning electron microscopy (SEM), and X-ray diffraction (XRD). Besides, the mineral residues were applied for adsorption of heavy metal ions.

Results and discussion

Results showed that the mycelia envelope the mineral and form fungal–mineral aggregates. The fungus can secrete a variety of organic acids including citric acid and oxalic acid; these attacked the surface and cleavage of biotite to release ions (Al³⁺, Fe³⁺, Mg²⁺, and K⁺). During incubation with A. niger, biotite weathered as shown by the relative decrease in biotite content and increase in interlayer spacing. Moreover, a certain concentration of phytic acid and tween-80 could promote the release of K⁺, and the fermentation liquid of rice bran has the same effect. Biotite residues showed a good adsorption for Cd²⁺, Pb²⁺, Zn²⁺, and Cu²⁺.

Conclusions

The results indicate that biotite can be biotransformed and release K⁺, of which the production can be acted as heavy metal ion adsorbent. It provides a reference for application of biotite in agriculture and control of heavy metal ion pollution in soil.

     

Remediation of polychlorinated biphenyl-contaminated soil by soil washing and subsequent TiO2 photocatalytic degradation

Purpose

An efficient method was developed for treating polychlorinated biphenyl (PCB)-contaminated soil by soil washing and subsequent TiO₂ photocatalytic degradation, and the photocatalytic degradation mechanism of PCBs was explored.

Materials and methods

Hydroxypropyl-??-cyclodextrin (HP??CD) and polyoxyethylene lauryl ether (Brij35) were used to extract PCBs from contaminated soil at first, and then the degradation of PCBs in the soil extracts was performed by TiO₂ photocatalysis under UV irradiation.

Results and discussion

Washing conditions including washing time, the concentration of HP??CD/Brij35, and the ratio of soil mass to solution volume for extracting 2,4,4??-trichlorobiphenyl (PCB28) from a PCB28-spiked soil were investigated at first. The results indicated that both HP??CD and Brij35 exhibited good performance. The intermediates of photocatalytic degradation of PCB28 were from its dechlorination and hydroxylation in the HPCD and aqueous solutions, respectively. A field PCB-contaminated soil from e-waste recycling sites was treated by this method. The results showed that the extracting percentage was significantly affected by the chlorination degree of PCBs, and HP??CD slowed down the photocatalytic degradation efficiency of overall PCBs.

Conclusions

Soil washing and subsequent TiO₂ photocatalytic degradation was successfully applied for treating PCB-contaminated soil, and HP??CD strongly altered the pathways of the photocatalytic degradation of PCBs.     

The role of stromatolites in explaining patterns of carbon, nitrogen, phosphorus, and silicon in the Se?ovlje saltern evaporation ponds (northern Adriatic Sea)

Purpose

In summer 2007, biweekly benthic fluxes of the biogenic elements carbon (C), nitrogen (N), silicon (Si), and phosphorus (P) were studied in the Se?ovlje saltern (salt-making facility) in the northern Adriatic Sea, Slovenia in order to determine the impact of stromatolite (??petola??) on the geochemical properties of saltern sediments.

Materials and methods

The brine and pore waters were analyzed for salinity, NH ₄ ⁺ , NO ₃ ^? , PO ₄ ^3? , SiO ₄ ^4? , total dissolved nitrogen, total dissolved phosphorus, and fluorescent dissolved organic matter. The sediment was analyzed for organic carbon (OC), total nitrogen (TN), total and organic phosphorus (OP), and biogenic Si concentrations, as well as values of ?? ¹³C_OC and ?? ¹⁵N_TN.

Results and discussion

Nutrient concentrations in brine water increased along the salinity gradient due to different processes, such as the evaporative concentrations of seawater, bacterial activity, more pronounced transformation and degradation of organic matter, and regeneration of nutrients. The petola from the Se?ovlje saltern, which is predominately composed of cyanobacterial and diatom communities, develops during the early evaporation stage and survives during high salinity and halite crystallization. Nitrogen fixation and P removal were the principal biogeochemical processes controlling dissolved inorganic N and P concentrations. At higher salinities, N limitation was more important. Microbes decomposed at higher salinities, and the remineralized N and P nutrients were released from surface pore waters to the brine. OP remineralization was also an important process influencing the distribution of PO ₄ ^3? concentrations in pore waters deeper in the sediments. The increasing SiO ₄ ^4? concentrations with increasing salinity in the brine waters were due to dissolution of diatom frustules, while the decrease in pore water SiO ₄ ^4? was probably the consequence of microbial uptake.

Conclusions

This study provides a better understanding of nutrient cycling and the geochemical processes in the Se?ovlje saltern.     

Comparison of the <Emphasis Type="Italic">Rhodotorula mucilaginosa</Emphasis> Biofilm and Planktonic Culture on Heavy Metal Susceptibility and Removal Potential

This study compares the effect of heavy metals (Hg²⁺, Cu²⁺, and Pb²⁺) on the Rhodotorula mucilaginosa and Saccharomyces boulardii biofilm and planktonic cells. A MBEC^TM-HTP assay was used to test the levels of tolerance to heavy metals. The minimum inhibitory concentration (MICp) and minimum lethal concentration (MLCp) of the R. mucilaginosa and S. boulardii planktonic cells were determined, as well as minimum biofilm eradication concentration (MBEC). Metal removal efficiency was determined by batch biosorption assay. Previous studies had focused on heavy metal tolerance and removal efficiency of planktonic cells from Rhodotorula species only. Hence, our study presents and compares results for metal tolerance and removal efficiency of the R. mucilaginosa planktonic cells and biofilm. Biofilm tolerance was higher than the planktonic cells. The R. mucilaginosa planktonic cells showed the tolerance in the presence of Hg²⁺ (MICp 0.08 mM), Cu²⁺ (MICp 6.40 mM), and Pb²⁺ (MICp 3.51 mM), while the S. boulardii planktonic cells only tolerated Pb²⁺ (MICp 0.43 mM). The R. mucilaginosa biofilm showed the highest tolerance in the presence of Hg²⁺ (MBEC >0.31 mM), Cu²⁺(MBEC >12.81 mM), Pb²⁺ (MBEC >7.12 mM), and obtained results were confirmed by fluorescence microscopy. S. boulardii did not show potential in biofilm formation. The R. mucilaginosa biofilm exhibited better efficiency in removal of all tested metals than the planktonic cells. Metal removal efficiency was in the range from 4.79–10.25% for planktonic cells and 91.71–95.39% for biofilm.     

Effects of Land Use on Hydrochemistry and Contamination of Karst Groundwater from Nandong Underground River System, China

The Nandong Underground River System (NURS) is located in Southeast Yunnan Province, China. Groundwater in NURS plays a critical role in socio-economical development of the region. However, with the rapid increase of population in recent years, groundwater quality has degraded greatly. In this study, the analysis of 36 groundwater samples collected from springs in both rain and dry seasons shows significant spatial disparities and slight seasonal variations of major element concentrations in the groundwater. In addition, results from factor analysis indicate that NO ₃ ^? , Cl^?, SO ₄ ^2? , Na⁺, K⁺, and EC in the groundwater are mainly from the sources related to human activities while Ca²⁺, Mg²⁺, HCO ₃ ^? , and pH are primarily controlled by water–rock interactions in karst system with Ca²⁺ and HCO ₃ ^? somewhat from anthropogenic inputs. With the increased anthropogenic contaminations, the groundwater chemistry changes widely from Ca-HCO₃ or Ca (Mg)-HCO₃ type to Ca-Cl (+NO₃) or Ca (Mg)-Cl (+NO₃), and Ca-Cl (+NO₃+SO₄) or Ca (Mg)-Cl (+NO₃+SO₄) type. Concentrations of NO ₃ ^? , Cl^?, SO ₄ ^2? , Na⁺, and K⁺ generally show an indistinct grouping with respect to land use types, with very high concentrations observed in the groundwater from residential and agricultural areas. This suggests that those ions are mainly derived from sewage effluents and fertilizers. No specific land use control on the Mg²⁺ ion distribution is observed, suggesting Mg²⁺ is originated from natural dissolution of carbonate rocks. The distribution of Ca²⁺ and HCO ₃ ^? does not show any distinct land use control either, except for the samples from residential zones, suggesting the Ca²⁺ and HCO ₃ ^- mainly come from both natural dissolution of carbonate rocks and sewage effluents.     

Quantification of seasonal sediment and phosphorus transport dynamics in an agricultural watershed using radiometric fingerprinting techniques

Purpose

Phosphorus (P) is a limiting nutrient for most US Midwestern aquatic systems and, therefore, increases of P, through point or non-point sources (NPS) of pollution such as agriculture, causes eutrophication. Identifying specific NPS contributions (e.g., upland vs. stream channels) for sediments and P is difficult due to the distributed nature of the pollution. Therefore, studies which link the spatial and temporal aspects of sediment and P transport in these systems can help better characterize the extent of NPS pollution.

Materials and methods

Our study used fingerprinting techniques to determine sources of sediments in an agricultural watershed (the North Fork of the Pheasant Branch watershed; 12.4 km² area) in Wisconsin, USA, during the spring, summer, and fall seasons of 2009. The primary sources considered were uplands (cultivated fields), stream bank, and streambed. The model used fallout radionuclides, ¹³⁷Cs, and ²¹⁰Pb_xs, along with total P to determine primary sediment sources. A shorter-lived fallout radioisotope, ⁷Be, was used to determine the sediment age and percent new sediments in streambed and suspended sediment samples (via the ⁷Be/²¹⁰Pb_xs ratio).

Results and discussion

Upland areas were the primary source of suspended sediments in the stream channels followed by stream banks. The sediment age and percent new sediment for the streambed and suspended sediments showed that the channel contained and transported newer (or more recently tagged with ⁷Be) sediments in the spring season (9–131 days sediment age), while relatively old sediments (165–318 days) were moving through the channel system during the fall season.

Conclusions

Upland areas are the major contributors to in-stream suspended sediments in this watershed. Sediment resuspension in stream channels could play an important role during the later part of the year. Best management practices should be targeted in the upland areas to reduce the export of sediments and sediment-bound P from agricultural watersheds.     

Intercomparison of snow Sampling and Analysis Within the Alpine-Wide Snowpack Investigation (SNOSP)

In order to investigate the seasonal and geographical distribution of snow concentrations anddeposition fluxes of environmentally relevant ionic species in the Alps, the international programSNOSP was initiated. In the framework of this program, intercomparisons of snow samplingtechniques and analytical methods to determine the ionic species C1^-, NO ₃ ^- ,SO ₄ ^2- , K⁺, Na⁺, NH4 ⁺, Mg²⁺, and Ca²⁺, as well as the pH and the specificconductivity were performed. The concentrations of these species in the snow samples collectedin the SNOSP program varied by orders of magnitude with, e.g., concentrations of NO ₃ ^- , SO ₄ ^2- , and NH4 ⁺ ranging from 0.2-60, 0.2-90, and 0.1-60 µeq L^-1,respectively. The intercomparisons revealed a reasonable agreement of the determinations of thespecies Cl^-, NO ₃ ^- , SO ₄ ^2- , Na⁺, and NH4 ⁺ in snow. Results were less satisfactory for K⁺, Mg²⁺, Ca²⁺,and H⁺, mainly due to the very low concentrations. In conclusion, recommendations areformulated for the reliable derivation of chemical inventories from snow packs.     

Degradation Kinetics of an Aged Hydrocarbon-Contaminated Soil

PM2.5 and PM10 samples were collected in the urban atmosphere of Elche (southeastern Spain) between December 2004 and November 2005. The samples were analyzed for mass and water-soluble inorganic ions (Na⁺, ${\text{NH}}^{{\text{ + }}}_{{\text{4}}}$ , K⁺, Ca²⁺, Mg²⁺, Cl^?, ${\text{NO}}^{{\text{ - }}}_{{\text{3}}}$ and ${\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}}$ ) with the aim of investigating the influence of the climatic and geographic features of a coastal semiarid area on the contribution of these species to PM levels. Secondary inorganic ions ( ${\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}}$ , ${\text{NO}}^{{\text{ - }}}_{{\text{3}}}$ , ${\text{NH}}^{{\text{ + }}}_{{\text{4}}}$ ) were the major components in the fine fraction (PM2.5), accounting for 40% of the total mass. The relationship between non-marine ${\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}}$ and ${\text{NH}}^{{\text{ + }}}_{{\text{4}}}$ indicated that fine sulfate particles were completely neutralized by ammonium. In the coarse fraction (PM10–2.5), nitrate (as NaNO₃ and Ca(NO₃)₂), together with crustal (CaCO₃) and marine species (NaCl) accounted for almost 50% of the total mass. Fine sulfate and coarse nitrate showed summer maximums. In contrast, the concentrations of fine ${\text{NO}}^{{\text{ - }}}_{{\text{3}}}$ were lowest in the warm period. Ammonium presented both winter and summer maximums. The levels of marine ions, except for coarse Cl^?, were highest in summer when the dominant wind flow is from the sea. No significant seasonal variations were observed for coarse Ca²⁺ and ${\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}}$ . The concentrations of all inorganic ions increased during Saharan dust events, in particular, fine ${\text{NH}}^{{\text{ + }}}_{{\text{4}}}$ and ${\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}}$ and coarse $NO_3^ - $ . Coarse calcium was proved not to be a good tracer for this type of episode in our region since the average levels of this cation are elevated and the relative increase in its concentrations during African events was not as high as expected.     

Mid-term trends in acid precipitation,streamwater chemistry and element budgets in the strengbach catchment (Vosges Mountains,France)

In the Vosges Mountains (NE of France), integrated plot-catchment studies have been carried out since 1985 in the Strengbach basin to study the influence of acid atmospheric inputs on surface water quality and element budgets. In this paper, available mid-term time series (1985–1991) have been considered to detect obvious trends, if any, in surface water chemistry and element budgets. Air quality data showed a slight decline for SO₂, whereas NO₂ slightly increased over the period, but these trends are not very significant. This is in agreement with increased N concentration (mainly as NH ₄ ⁺ ) and with the stability of SO ₄ ^2? in open field precipitation. Because of a significant decrease in rainfall amount over the period, only inputs of NH ₄ ⁺ increased significantly whereas H⁺ and SO ₄ ²⁺ inputs declined. In spring and streamwaters, pH and dissolved Si concentration increased mainly as a result of a reduced flow. Na⁺, K⁺, Cl^? and HCO-3~^? concentrations remained stable whereas Ca²⁺, Mg²⁺ and SO ₄ ²⁺ concentrations declined significantly. Only NO ₃ ^? concentration increased significantly in springwaters. The catchment budgets revealed significant losses of base cations, Si and SO ₄ ^2? . These losses decreased over the period. Nitrogen was retained in the ecosystem. However, a longer record is needed to determine whether or not changes in surface water chemistry have resulted from short-term flow reductions or long-term changes in input-output ion budgets. This is specially true with N because the decline in SO ₄ ^2? output was accompanied by N accumulation.     

Effective Removal of Toxic Heavy Metal Ions from Aqueous Solution by CaCO<Subscript>3</Subscript> Microparticles

Heavy metals are a common contaminant in water supplies and pose a variety of serious health risks to nearby human populations. A promising approach to heavy metal decontamination is the sequestration of heavy metal ions in porous materials; however, current technologies involve materials which can be difficult to synthesize, are high-cost, or are themselves potentially toxic. Herein, we demonstrate that rapidly synthesized calcium carbonate (CaCO₃) microparticles can effectively remove high quantities of Pb²⁺, Cd²⁺, and Cu²⁺ ions (1869, 1320, and 1293 mg per gram of CaCO₃ microparticles, respectively) from aqueous media. The CaCO₃ microparticles were characterized with powder X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and Brunauer–Emmett–Teller (BET) N₂ sorption–desorption. It was found that the Ca²⁺ ions of the microparticles were replaced by the heavy metal ions, leading to partially recrystallized nanoparticles of new compositional phases such as cerussite (PbCO₃). The adsorption, surface dissolution/re-precipitation, and nucleation/crystal growth mechanisms were determined by investigating the Ca²⁺ released, along with the changes to particle morphology and crystal structure. Importantly, this study demonstrates that the porous CaCO₃ microparticles performed well in a system with multiple heavy metal ion species: 100% of Cu²⁺, 97.5% of Pb²⁺, and 37.0% Cd²⁺ were removed from an aqueous solution of all cations with initial individual metal concentrations of 50 mg/L and 1.5 g/L of CaCO₃ microparticles. At this concentration, the CaCO₃ microparticles significantly outperformed activated carbon. These results help to establish CaCO₃ microparticles as a promising low-cost and scalable technology for removing heavy metal ions from contaminated water.

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Graphical abstract ?

     

Influence of Catchment Characteristics and Flood Type on Relationship Between Streamwater Chemistry and Streamflow: Case Study from Carpathian Foothills in Poland

The study aimed to determine the influence of catchment characteristics and flood type on the relationship between streamflow and a number of chemical characteristics of streamwater. These were specific electrical conductivity (SC), pH, the concentrations of main ions (Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO ₃ ^? , SO ₄ ^2? , and Cl^?), and nutrients (NH ₄ ⁺ , NO ₂ ^? , NO ₃ ^? , and PO ₄ ^3? ). These relationships were studied in three small catchments with different geological structure and land use. Several flood types were distinguished based on the factors that initiate flooding and specific conditions during events. Geological factors led to a lower SC and main ion concentrations at a given specific runoff in catchments built of resistant sandstone versus those built of less resistant sediments. A lower concentration of nutrients was detected in the semi-natural woodland catchment versus agricultural and mixed-use catchments, which are strongly impacted by human activity. The strongest correlation between streamflow and the chemical characteristics of water was found in the woodland catchment. Different types of floods were characterized by different ion concentrations. In the woodland catchment, higher SC and higher concentrations of most main ions were noted during storm-induced floods than during floods induced by prolonged rainfall. The opposite was true for the agricultural and mixed-use catchments. During snowmelt floods, SC, NO ₃ ^? , and most main ion concentrations were higher when the soil was unfrozen in the agricultural and mixed-use catchments versus when the soil was frozen. In the case of the remaining nutrients, lower concentrations of NH ₄ ⁺ were detected during rain-induced floods than during snowmelt floods. The opposite was true of PO ₄ ^3? .     

Evaluation of different fractions of the organic matter of peat on tetracycline retention in environmental conditions: in vitro studies

Purpose

Due to the modernization of the agro-industrial sector, compounds with different toxicity and effects on human health and animal have been used and consequently affecting the environment. Among them, tetracycline (TC) stands out as one of the antibiotics most commonly used worldwide. This study evaluated the TC interaction with different fractions of peat in natura and humic substances, humic acid, fulvic acid, and humin.

Materials and methods

The different fractions of the organic matter were characterized by organic matter content, elemental analysis, spectroscopic analysis (E₄/E₆), and nuclear magnetic resonance of carbon 13 (NMR ¹³C), and the interaction between TC and different fractions of organic matter was made by fluorescence spectrometry. We used the tangential ultra-filtration system for determining the complexation capability of humic substances (HSs), fulvic acids (FA), humic acids (HA), and humin (HUM) from peat with TC. Finally, we evaluated sorption kinetic experiments between TC and peat in natura.

Results and discussion

The peat samples, humic substances, FAs, HAs, and HUM were characterized by organic matter (OM), atomic ratio (H/C and C/O) calculated from elemental analysis data, functional groups quantified by NMR ¹³C data, and E₄/E₆ ratio, and the results show significant differences in the structural characteristics of the fractions of OM influenced by the type of microorganisms and environmental factors associated with this decomposition. Data analysis revealed the strongest interaction between HUM and TC (59.19 mg g^?1), followed by interaction between HS and TC (43.36 mg g^?1 HS). In the sorption studies, these conditions showed the best model to describe the system under consideration using the Freundlich model.

Conclusions

The results showed that the different fractions of the OM extracted from peat show different contributions that affect the bioavailability of contaminants to the environment.

     

Biotic and abiotic processes controlling water chemistry during snowmelt at rabbit ears pass,Rocky Mountains,Colorado, U.S.A.

The chemical composition of snowmelt, groundwater, and streamwater was monitored during the spring of 1991 and 1992 in a 200-ha subalpine catchment on the western flank of the Rocky Mountains near Steamboat Springs, Colorado. Most of the snowmelt occurred during a one-month period annually that began in mid-May 1991 and mid-April 1992. The average water quality characteristics of individual sampling sites (meltwater, streamwater, and groundwater) were similar in 1991 and 1992. The major ions in meltwater were differentially eluted from the snowpack, and meltwater was dominated by Ca²⁺, SO ₄ ^2? , and NO ₃ ^? . Groundwater and streamwater were dominated by weathering products, including Ca²⁺, HCO ₃ ^? (measured as alkalinity), and SiO₂, and their concentrations decreased as snowmelt progressed. One well had extremely high NO ₃ ^? . concentrations, which were balanced by Ca²⁺ concentrations. For this well, hydrogen ion was hypothesized to be generated from nitrification in overlying soils, and subsequently exchanged with other cations, particularly Ca²⁺. Solute concentrations in streamwater also decreased as snowmelt progressed. Variations in groundwater levels and solute concentrations indicate that most of the meltwater traveled through the surficial materials. A mass balance for 1992 indicated that the watershed retained H⁺, NH ₄ ⁺ , NO ₃ ^? , SO ₄ ^2? and Cl^? and was the primary source of base cations and other weathering products. Proportionally more SO ₄ ^2? was deposited with the unusually high summer rainfall in 1992 compared to that released from snowmelt, whereas NO ₃ ^? was higher in snowmelt and Cl^? was the same. The sum of snowmelt and rainfall could account for greater than 90% of the H⁺ and NH ₄ ⁺ retained by the watershed and greater than 50% of the NO ₃ ^? .     

Photodegradation of Sulfamethoxazole Applying UV- and VUV-Based Processes

The efficiency of UV- and VUV-based processes (UV, VUV, UV/H₂O₂, and VUV/H₂O₂) for removal of sulfamethoxazole (SMX) in Milli-Q water and sewage treatment plant (STP) effluent was investigated at 20??C. The investigated factors included initial pH, variety of inorganic anions (NO ₃ ^? and HCO ₃ ^? ), and humic acid (HA). The results showed that the degradation of SMX in Milli-Q water at both two pH (5.5 and 7.0) followed the order of VUV/H₂O₂ > VUV > UV/H₂O₂ > UV. All the experimental data well fitted the pseudo-first order kinetic model and the rate constant (k) and half-life time (t _1/2) were determined accordingly. Indirect oxidation of SMX by generated ^?OH was the main degradation mechanism in UV/H₂O₂ and VUV/H₂O₂, while direct photolysis predominated in UV processes. The quenching tests showed that some other reactive species along with ^?OH radicals were responsible to the SMX degradation under VUV process. The addition of 20?mg?L^?1 HA significantly inhibited SMX degradation, whereas, the inhibitive effects of NO ₃ ^? and HCO ₃ ^? (0.1?mol?L^?1) were observed as well in all processes except in UV irradiation for NO ₃ ^? . The removal rate decreased 1.7?C3.6 times when applying these processes to STP effluent due to the complex constituents, suggesting that from the application point of view the constituents of these complexes in real STP effluent should be considered carefully prior to the use of UV-based processes for SMX degradation.     

Examination of the Dissolved Inorganic Nitrogen Budget in Three Experimental Microbasins with Contrasting Land Cover—A Mass Balance Approach

A long-term hydrological and water chemistry research was conducted in three experimental microbasins differing in land cover: (1) a purely agricultural fertilized microbasin, (2) a forested microbasin dominated by Carpinus betulus (European hornbeam), and (3) a forested microbasin dominated by Picea abies (L.) (Norway spruce). The dissolved inorganic nitrogen (DIN: NH ₄ ⁺ , NO ₂ ^? , NO ₃ ^? ) budget was examined for a period of 3 years (1991–1993). Mean annual loads of DIN along with sulfate SO ₄ ^2? and base cations Ca²⁺, Mg²⁺, Na⁺, K⁺, and HCO ₃ ^? were calculated from ion concentrations measured in stream water, open-area rainfall, throughfall (under tree canopy), and streamwater at the outlets from the microbasins. Comparison of the net imported/exported loads showed that the amount of NO ₃ ^? leached from the agricultural microbasin is ～3.7 times higher (43.57 kg ha^?1?a^?1) than that from the spruce dominated microbasin (11.86 kg ha^?1?a^?1), which is a markedly higher export of NO ₃ ^? compared to the hornbeam dominated site. Our analyses showed that land cover (tree species) and land use practices (fertilization in agriculture) may actively affect the retention and export of nutrients from the microbasins, and have a pronounce impact on the quality of streamwater. Sulfate export exceeded atmospheric rainfall inputs (measured as wet deposition) in all three microbasins, suggesting an additional dry depositions of SO ₄ ^2? and geologic weathering.     

Evolution and phosphorus fractionation in saline Spolic Technosols flooded with eutrophic water

Purpose

The aim of this study was to evaluate the behaviour of P in saline Spolic Technosols flooded with eutrophic water, with and without plant rhizosphere, in order to assess the role of these soils as sinks or sources of this nutrient.

Materials and methods

Samples were taken from basic (pH?~7.8), carbonated and acidic (pH?~6.2), de-carbonated soils of salt marshes polluted by mine wastes. Three treatments were assayed: pots with Sarcocornia fruticosa, pots with Phragmites australis and pots without plants (bare soil). The pots were flooded for 15?weeks with eutrophic water (PO ₄ ^3? ~6.92?mg?L^?1) and pH, Eh and water-soluble organic carbon and PO ₄ ^3? concentrations were monitored in the soil solution. A soil P fractionation was applied before and after the flooding period.

Results and discussion

The PO ₄ ^3? concentration in the soil solution decreased rapidly in both soils, with and without plant, being diminished by 80?C90?% after 3?h of flooding. The Fe/Mn/Al oxides and the Ca/Mg compounds played an important role in soil P retention. In pots with S. fruticosa, the reductive conditions due to flooding induced P release from metal oxides and P retention to Ca/Mg compounds. In turn, P. australis may have favoured the release of P from carbonates, which was transferred to Fe/Mn/Al compounds.

Conclusions

The retention of P by the soil was the main mechanism involved in the removal of PO ₄ ^3? from the eutrophic flooding water but to evaluate the capacity of these systems as long-term P sinks, the combined effect of metals, Ca/Mg compounds and specific plant species should be considered.     

Comprehensive study of Pb (II) speciation in soil by X-ray absorption spectroscopy (XANES and EXAFS) and sequential fractionation

Purpose

The study is aimed at the analysis of the spatial–structural organization of Pb(II) in Chernozem soils and the relationship between the metal ion and the soil components using X-ray absorption spectroscopy and chemical extractive fractionation.

Materials and methods

In a model experiment, soil samples were artificially contaminated with elevated rates of Pb(NO₃)₂ and PbO (2000 and 10,000 mg kg^?1). The samples of mineral phases (bentonite, gibbsite, kaolinite, calcite, and hydromuscovite) were saturated with Pb²⁺ ions. The sequential fractionation of Pb in the soil was conducted by the Tessier method. X-ray absorption near-edge fine structure (XANES) spectra at the Pb L_III-edge (13.040 keV) were obtained on a Rigaku R-XAS Looper spectrometer. Extended X-ray absorption fine structure (EXAFS) L_III-edge Pb was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation.

Results and discussion

The results of successive extraction showed that Pb is associated with strongly bound organic substances, Fe and Mn (hydr)oxides, and carbonates. An increase in the portion of exchangeable fraction is observed under extreme loads. At the addition of Pb in the form of oxide and nitrate to the soil, the fractional compositions were similar, which indicates the good transformation of PbO in Chernozem. The features of XANES spectra indicate different orbital transitions in the electron shells of Pb²⁺ ions for monoxide (PbO) and soluble salt (Pb(NO₃)₂), which affect the ion properties and determine the individual structure of the coordination sphere. The analysis of XANES revealed that sorption of Pb in the soil samples and in the samples of mineral phases does not change its bond valence.

Conclusions

The increased degree of soil contamination with Pb is accompanied by decreasing the stable connection between metal and soil components. Lead ions in bentonite, kaolinite, hydromuscovite, gibbsite, and calcite are incorporated in the positions of the inner-sphere complex replacing some aluminum ions in the octahedral sites. This results in changes the Pb–O distances in Pb-bearing octahedrons. We may suggest that Pb²⁺ is also sorbed by dimer (Pb–Pb) silicate and/or aluminum groups. The structure of adsorbent surface plays the key role in the sorption of Pb²⁺ by mineral phases.