Colloid-facilitated transport of lead in natural discrete fractures

Colloid-facilitated transport of lead (Pb) was explored in a natural chalk fracture with an average equivalent hydraulic aperture of 139 μm. Tracer solution was prepared by adding montmorillonite (100 mg L^?1) and/or humic acid (HA) (10 mg L^?1) to modified artificial rainwater containing dissolved Pb (21.4 mg Pb L^?1), naturally precipitated PbCO₃ particles (16.4 mg Pb L^?1) and LiBr (39.0 mg L^?1). We found that Pb is only mobile when associated with colloids. PbCO₃ particles were not mobile in the fracture. The addition of HA to the montmorillonite suspension increased the suspension's mobility and therefore promoted the colloid-facilitated transport of Pb. The increases in pH and sodium absorption ratio induced by the chalk-tracer solution interactions appeared to increase the dispersion and mobilization of colloids entering the fracture. The dominant colloid-facilitated transport of Pb reported in this study has significant implications for risk assessment of Pb mobility in fractured rocks.     

Dual mechanochemical immobilization of heavy metals and decomposition of halogenated compounds in automobile shredder residue using a nano-sized metallic calcium reagent

Simultaneous immobilization of heavy metals and decomposition of halogenated organic compounds in different fractions of automobile shredder residue (ASR) were achieved with a nano-sized metallic calcium through a 60-min ball milling treatment. Heavy metal (HM) immobilization and chlorinated/brominated compound (CBC) decomposition efficiencies both reached 90–100 %, after ball milling with nanometallic calcium/calcium oxide (Ca/CaO) dispersion, regardless of ASR particle size (1.0, 0.45–1.0, and 0.250 mm). Concentrations of leachable HMs substantially decreased to a level lower than the regulatory standard limits (Co and Cd 0.3 mg L⁻¹; Cr 1.5 mg L⁻¹; Fe, Pb, and Zn 3.0 mg L⁻¹; Mn and Ni 1 mg L⁻¹) proposed by the Korean hazardous waste elution standard regulatory threshold. Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) element maps/spectra showed that while the amounts of HMs and CBCs detectable in ASR significantly decreased, the calcium mass percentage increased. X-ray powder diffraction (XRD) patterns indicate that the main fraction of enclosed/bound materials on ASR includes Ca-associated crystalline complexes that remarkably inhibit HM desorption and simultaneously transform dangerous CBCs into harmless compounds. The use of a nanometallic Ca/CaO mixture in a mechanochemical process to treat hazardous ASR (dry conditions) is an innovative approach to remediate cross-contaminated residues with heavy metals and halogenated compounds.

     

Heavy metal bioaccumulation by wild edible saprophytic and ectomycorrhizal mushrooms

Heavy metals cause serious problems in the environment, and they can be accumulated in organisms, especially in the higher fungi. The concentration of Ni, Cr, Pb, Cd, and Hg in 10 species of edible mushrooms in Medvednica Nature Park, Croatia was therefore determined. In addition, the similarity between the studied species was determined by cluster analysis based on concentrations of the aforementioned metals in the fruiting bodies. The contents of nickel, chromium, lead, cadmium, and mercury in the fruiting bodies of mushrooms were obtained by X-ray fluorescence spectrometry. The highest concentrations of Ni (3.62 mg kg^?1), Cr (3.01 mg kg^?1), and Cd (2.67 mg kg^?1) were determined in Agaricus campestris. The highest concentration of Pb (1.67 mg kg^?1) was determined in Macrolepiota procera, and the highest concentration of Hg (2.39 mg kg^?1) was determined in Boletus edulis. The concentration of all heavy metals significantly differed (p?<?0.001) between examined saprophytic and ectomycorrhizal mushrooms. Considering anatomical part of the fruiting body (cap-stipe), a considerably higher concentration of the analyzed elements was found in the cap for all mushroom species. According to calculated bioconcentration factors, all the examined species were found to be bioexclusors of Ni, Cr, and Pb and bioaccumulators of Cd and Hg. Cluster analysis performed on the basis of the accumulation of the studied metals revealed great phenotypic similarity of mushroom species belonging to the same genus and partial similarity of species of the same ecological affiliation.

     

Acute and chronic effects of nano- and non-nano-scale TiO2 and ZnO particles on mobility and reproduction of the freshwater invertebrate Daphnia magna

Among the emerging literature addressing the biological effects of nanoparticles, very little information exists, particularly on aquatic organisms, that evaluates nanoparticles in comparison to non-nanocounterparts. Therefore, the potential effects of nano-scale and non-nano-scale TiO₂ and ZnO on the water flea, Daphnia magna, were examined in 48-h acute toxicity tests using three different test media, several pigment formulations – including coated nanoparticles – and a variety of preparation steps. In addition, a 21-d chronic Daphnia reproduction study was performed using coated TiO₂ nanoparticles. Analytical ultracentrifugation analyses provided evidence that the nanoparticles were present in a wide range of differently sized aggregates in the tested dispersions. While no pronounced effects on D. magna were observed for nano-scale and non-nano-scale TiO₂ pigments in 19 of 25 acute (48-h) toxicity tests (EC50 > 100 mg L⁻¹), six acute tests with both nano- and non-nano-scale TiO₂ pigments showed slight effects (EC10, 0.5–91.2 mg L⁻¹). For the nano-scale and non-nano-scale ZnO pigments, the acute 48-h EC50 values were close to the 1 mg L⁻¹ level, which is within the reported range of zinc toxicity to Daphnia. In general, the toxicity in the acute tests was independent of particle size (non-nano-scale or nano-scale), coating of particles, aggregation of particles, the type of medium or the applied pre-treatment of the test dispersions. The chronic Daphnia test with coated TiO₂ nanoparticles demonstrated that reproduction was a more sensitive endpoint than adult mortality. After 21 d, the NOEC for adult mortality was 30 mg L⁻¹ and the NOEC for offspring production was 3 mg L⁻¹. The 21-d EC10 and EC50 values for reproductive effects were 5 and 26.6 mg L⁻¹, respectively. This study demonstrates the utility of evaluating nanoparticle effects relative to non-nano-scale counterparts and presents the first report of chronic exposure to TiO₂ nanoparticles in D. magna.     

Influence of earthworm mucus and amino acids on tomato seedling growth and cadmium accumulation

The effects on the growth of tomato seedlings and cadmium accumulation of earthworm mucus and a solution of amino acids matching those in earthworm mucus was studied through a hydroponic experiment. The experiment included four treatments: 5 mg Cd L⁻¹ (CC), 5 mg Cd L⁻¹ + 100 mL L⁻¹ earthworm mucus (CE), 5 mg Cd L⁻¹ + 100 mL L⁻¹ amino acids solution (CA) and the control (CK). Results showed that, compared with CC treatment, either earthworm mucus or amino acids significantly increased tomato seedling growth and Cd accumulation but the increase was much higher in the CE treatment compared with the CA treatment. This may be due to earthworm mucus and amino acids significantly increasing the chlorophyll content, antioxidative enzyme activities, and essential microelement uptake and transport in the tomato seedlings. The much greater increase in the effect of earthworm mucus compared with amino acid treatments may be due to IAA-like substances in earthworm mucus.     

Phytotoxicity of 15 common pharmaceuticals on the germination of Lactuca sativa and photosynthesis of Chlamydomonas reinhardtii

Pharmaceuticals reach terrestrial environments through the application of treated wastewaters and biosolids to agricultural soils. We have investigated the toxicity of 15 common pharmaceuticals, classified as nonsteroidal anti-inflammatory drugs (NSAIDs), blood lipid-lowering agents, β-blockers and antibiotics, in two photosynthetic organisms. Twelve pharmaceuticals caused inhibitory effects on the radicle and hypocotyl elongation of Lactuca sativa seeds. The EC₅₀ values obtained were in the range of 170–5656 mg L⁻¹ in the case of the radicle and 188–4558 mg L⁻¹ for the hypocotyl. Propranolol was the most toxic drug for both root and hypocotyl elongation, followed by the NSAIDs, then gemfibrozil and tetracycline. Other effects, such as root necrosis, inhibition of root growth and curly hairs, were detected. However, even at the highest concentrations tested (3000 mg L⁻¹), seed germination was not affected. NSAIDs decreased the photosynthetic yield of Chlamydomonas reinhardtii, but only salicylic acid showed EC₅₀ values below 1000 mg L⁻¹. The first effects detected at low concentrations, together with the concentrations found in environmental samples, indicate that the use of biosolids and wastewaters containing pharmaceuticals should be regulated and their compositions assessed in order to prevent medium- and long-term impacts on agricultural soils and crops.

     

Microtubule integrity and cell viability under metal (Cu,Ni and Cr) stress in the seagrass Cymodocea nodosa

The effects of increasing Cu, Ni and Cr concentrations (0.5, 5, 10, 20 and 40 mg L⁻¹) on microtubule organization and the viability of leaf cells of the seagrass Cymodocea nodosa for 13 consecutive days were investigated under laboratory conditions. Increased oblique microtubule orientation, microtubule depolymerization at the 5–40 mg L⁻¹ Ni treatments after 3 d of exposure, and a complete microtubule depolymerization at all Ni treatments after 5 d were observed. Cu depolymerised microtubules after three to 7 d of exposure, while Cr caused an extensive microtubule bundling after 9 or 11 d of exposure, depending on metal dosage. Fluorescence intensity measurements further consolidated the above phenomena. Cell death, occurring at later time than microtubule disturbance, was also observed at all Cu and Ni treatments and at the 10–40 mg L⁻¹ Cr treatments and adding to the above quantification of the number of dead cells clearly showed that only a portion of the cell population studied died. The data presented, being the first assessment of microtubule disturbance in seagrasses, indicate that microtubules in seagrass leaf cells could be used as a valuable and early marker of metal-induced stress in biomonitoring programmes.     

Derivation of aquatic predicted no-effect concentration (PNEC) for 2,4-dichlorophenol: comparing native species data with non-native species data

2,4-Dichlorophenol (2,4-DCP) is known as an important chemical intermediate and an environmental endocrine disruptor. There is no paper dealing with the predicted no-effect concentration (PNEC) of 2,4-DCP, mainly due to shortage of chronic and site-specific toxicity data. In the present study, toxicity data was obtained from the tests using six Chinese native aquatic species. The HC₅ (hazardous concentration for 5% of species) was derived based on the constructed species sensitivity distribution (SSD), which was compared with that derived from literature toxicity data of non-native species. For invertebrates, the survival no-observed effect concentrations (NOECs) were 0.05 and 1.00 mg L⁻¹ for Macrobrachium superbum and Corbicula fluminea, respectively. NOECs based on fishes’ growth were 0.10, 0.20 and 0.40 mg L⁻¹ for Mylopharyngodon piceus, Plagiognathops microlepis and Erythroculter ilishaeformis, respectively. For aquatic plant Soirodela polyrhiza, NOEC based on concentration of chlorophyll was 1.00 mg L⁻¹. A final PNEC calculated using the SSD approach with a 50% certainty based on different taxa ranged between 0.008 and 0.045 mg L⁻¹. There is no significant difference between HC₅ derived from native and that from non-native taxa.     

Emission factors and exposures from ground-level pyrotechnics

Potential exposures from ground-level pyrotechnics were assessed by air monitoring and developing emission factors. Total particulate matter, copper and SO₂ exposures exceeded occupational health guidelines at two outdoor performances using consumer pyrotechnics. Al, Ba, B, Bi, Mg, Sr, Zn, and aldehyde levels were elevated, but did not pose a health hazard based on occupational standards. Emission factors for total particulate matter, metals, inorganic ions, aldehydes, and polyaromatic hydrocarbons (PAHs) were determined for seven ground-supported pyrotechnics through air sampling in an airtight room after combustion. Particle generation ranged from 5 to 13% of the combusted mass. Emission factors (g Kg^?1) for metals common to pyrotechnics were also high: K, 23–45; Mg, 1–7; Cu, 0.05–7; and Ba, 0.03–6. Pb emission rates of 1.6 and 2.7% of the combusted mass for two devices were noteworthy. A high correlation (r² ≥ 0.89) between metal concentrations in pyrotechnic compositions and emission factors were noted for Pb, Cr, Mg, Sb, and Bi, whereas low correlations (r² ≤ 0.1) were observed for Ba, Sr, Fe, and Zn. This may be due to the inherent heterogeneity of multi-effect pyrotechnics. The generation of inorganic nitrogen in both the particulate (NO₂^?, NO₃^?) and gaseous (NO, NO₂) forms varied widely (<0.1–1000 mg Kg^?1). Aldehyde emission factors varied by two orders of magnitude even though the carbon source was carbohydrates and charcoal for all devices: formaldehyde (<7.0–82 mg Kg^?1), acetaldehyde (43–210 mg Kg^?1), and acrolein (1.9–12 mg Kg^?1). Formation of lower molecular weight PAHs such as naphthalene and acenaphthylene were favored, with their emission factors being comparable to that from the combustion of household refuse and agricultural debris. Ba, Sr, Cu, and Pb had emission factors that could produce exposures exceeding occupational exposure guidelines. Sb and unalloyed Mg, which are banned from consumer fireworks in the US, were present in significant amounts.     

Simultaneous reduction of Cr(VI) and oxidation of As(III) by Bacillus firmus TE7 isolated from tannery effluent

Hexavalent chromium [Cr(VI)] and arsenite [As(III)] are the most toxic forms of chromium and arsenic respectively, and reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) has great environmental implications as they affect toxicity and mobility of these toxic species. Bacillus firmus strain TE7, resistant to chromium and arsenic was isolated from tannery effluent. The strain exhibited ability to reduce Cr(VI) and oxidize As(III). It reduced 100 mg L^?1 Cr(VI) within 60 h in nutrient broth and oxidized 150 mg L^?1 As(III) within 10 h in minimal medium. It also completely reduced 15 mg L^?1 Cr(VI) and oxidized 50 mg L^?1 of As(III) simultaneously in minimal medium. To the best of our knowledge, this is the first bacterial strain showing simultaneous reduction of Cr(VI) and oxidation of As(III) and is a potential candidate for bioremediation of environments contaminated with these toxic metal species.     

Phytoextraction of Pb,Cr, Ni,and Zn using the aquatic plant Limnobium laevigatum and its potential use in the treatment of wastewater

In order to study the bioaccumulation of Pb, Cr, Ni, and Zn and the stress response, the floating aquatic plant Limnobium laevigatum was exposed to increasing concentrations of a mixture of these metals for 28 days, and its potential use in the treatment of wastewater was evaluated. The metal concentrations of the treatment 1 (T1) were Pb 1 μg L⁻¹, Cr 4 μg L⁻¹, Ni 25 μg L⁻¹, and Zn 30 μg L⁻¹; of treatment 2 (T2) were Pb 70 μg L⁻¹, Cr 70 μg L⁻¹, Ni 70 μg L⁻¹, and Zn 70 μg L⁻¹; and of treatment 3 (T3) were Pb 1000 μg L⁻¹, Cr 1000 μg L⁻¹, Ni 500 μg L⁻¹, and Zn 100 μg L⁻¹, and there was also a control group (without added metal). The accumulation of Pb, Cr, Ni, and Zn in roots was higher than in leaves of L. laevigatum, and the bioconcentration factor revealed that the concentrations of Ni and Zn in the leaf and root exceeded by over a thousand times the concentrations of those in the culture medium (2000 in leaf and 6800 in root for Ni; 3300 in leaf and 11,500 in root for Zn). Thus, this species can be considered as a hyperaccumulator of these metals. In general, the changes observed in the morphological and physiological parameters and the formation of products of lipid peroxidation of membranes during the exposure to moderate concentrations (T2) of the mixture of metals did not cause harmful effects to the survival of the species within the first 14 days of exposure. Taking into account the accumulation capacity and tolerance to heavy metals, L. laevigatum is suitable for phytoremediation in aquatic environments contaminated with moderated concentrations of Cr, Ni, Pb, and Zn in the early stages of exposure.

     

Hexavalent chromium reduction and plant growth promotion by Staphylococcusarlettae strain Cr11

Cr(VI), a mutagenic and carcinogenic pollutant in industrial effluents, was effectively reduced by an indigenous tannery effluent isolate Staphylococcus arlettae strain Cr11 under aerobic conditions. The isolate could tolerate Cr(VI) up to 2000 and 5000 mg L⁻¹ in liquid and solid media respectively. S. arlettae Cr11 effectively reduced 98% of 100 mg L⁻¹ Cr(VI) in 24 h. Reduction for initial Cr(VI) concentrations of 500 and 1000 mg L⁻¹ was 98% and 75%, respectively in 120 h. The isolate was also positive for siderophore, indole acetic acid, ammonia and catalase production, phosphate solubilization and biofilm formation in the presence and absence of Cr(VI). The isolate showed halotolerance (10% NaCl) and cross tolerance to other toxic heavy metals such as Hg²⁺, Ni²⁺, Cd²⁺ and Pb²⁺. Bacterial inoculation of Triticum aestivum in controlled petri dish and soil environment showed significant increase in percent germination, root and shoot length as well as dry and wet weight in Cr(VI) treated and untreated samples. This is the first report of simultaneous Cr(VI) reduction and plant growth promotion for a S. arlettae strain.     

Simultaneous E. coli inactivation and NOM degradation in river water via photo-Fenton process at natural pH in solar CPC reactor. A new way for enhancing solar disinfection of natural water

Bacteria inactivation and natural organic matter oxidation in river water was simultaneously conducted via photo-Fenton reaction at “natural” pH (6.5) containing 0.6 mg L⁻¹ of Fe³⁺ and 10 mg L⁻¹ of H₂O₂. The experiments were carried out by using a solar compound parabolic collector on river water previously filtered by a slow sand filtration system and voluntarily spiked with Escherichia coli. Fifty five percent of 5.3 mg L⁻¹ of dissolved organic carbon was mineralized whereas total disinfection was observed without re-growth after 24 h in the dark.     

A mass balance study of the phytoremediation of perchloroethylene-contaminated groundwater

A mass balance study was performed under controlled field conditions to investigate the phytoremediation of perchloroethylene (PCE) by hybrid poplar trees. Water containing 7–14 mg L^?1 PCE was added to the test bed. Perchloroethylene, trichloroethylene, and cis-dichloroethylene were detected in the effluent at an average of 0.12 mg L^?1, 3.9 mg L^?1, and 1.9 mg L^?1, respectively. The total mass of chlorinated ethenes in the water was reduced by 99%. Over 95% of the recovered chlorine was as free chloride in the soil, indicating near-complete dehalogenation of the PCE. Transpiration, volatilization, and accumulation in the trees were all found to be minor loss mechanisms. In contrast, 98% of PCE applied to an unplanted soil chamber was recovered as PCE in the effluent water or volatilized into the air. These results suggest that phytoremediation can be an effective method for treating PCE-contaminated groundwater in field applications.     

Effects of pH,initial Pb2+ concentration,and polyculture on lead remediation by three duckweed species

Various geographical duckweed isolates have been developed for phytoremediation of lead. The Pb²⁺ removal efficiency of Lemna aequinoctialis, Landoltia punctata, and Spirodela polyrhiza was investigated in monoculture and polyculture at different levels of pH and initial Pb²⁺ concentrations. L. aequinoctialis was not sensitive to the tested pH but significantly affected by initial Pb²⁺ concentration, whereas synergistic effect of pH and initial Pb²⁺ concentration on removal efficiency of L. punctata and S. polyrhiza was found. Although the majority of polycultures showed median removal efficiency as compared to respective monocultures, some of the polycultures achieved higher Pb²⁺ removal efficiencies and can promote population to remove Pb²⁺. Besides, the three duckweed strains could be potential candidates for Pb²⁺ remediation as compared to previous reports. Conclusively, this study provides useful references for future large-scale duckweed phytoremediation.

     

Evaluation of exposure to fluoride in child population of North Argentina

Fluoride is an important element for humans. It inhibits initiation and progression of dental caries and stimulates bone formation. However, excessive intake may lead to the appearance of dental and/or skeletal fluorosis and a decrease in intellectual coefficient in child populations. This study evaluates exposure to fluoride in the child population of Chaco province (Argentina) by analysis of drinking water, food and its bioaccessible fraction (quantity of fluoride solubilised by gastrointestinal digestion and available for intestinal absorption) and urine as a biomarker of internal dose. The concentration of fluoride in drinking water varied between 0.050 and 4.6 mg L^?1, and 80% of the samples exceeded the WHO drinking-water guideline value (1.5 mg L^?1). Fluoride concentrations in food ranged between 0.80 and 3.0 mg kg^?1 fresh weight (fw), being lower in bioaccessible fraction (0.43–1.9 mg kg^?1, fw). On the basis of the consumption data declared for the young child population, fluoride intake varies between 4.1 and 6.5 mg day^?1, greater than the level recommended for this age group. Moreover, in some cases, concentrations of fluoride found in urine (0.62–8.9 mg L^?1) exceeded those reported in areas with declared fluorosis. All data obtained show the worrying situation of child population in this area of Argentina.

     

Ecotoxicity evaluation of selected sulfonamides

Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀ = 1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀ = 0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀ = 2.59 mg L⁻¹).     

Effects of sediment burial disturbance on macro and microelement dynamics in decomposing litter of <Emphasis Type="Italic">Phragmites australis</Emphasis> in the coastal marsh of the Yellow River estuary,China

From April 2008 to November 2009, a field decomposition experiment was conducted to investigate the effects of sediment burial on macro (C, N) and microelement (Pb, Cr, Cu, Zn, Ni, and Mn) variations in decomposing litter of Phragmites australis in the coastal marsh of the Yellow River estuary. Three one-off sediment burial treatments [no sediment burial (0 mm year^?1, S₀), current sediment burial (100 mm year^?1, S₁₀), and strong sediment burial (200 mm year^?1, S₂₀)] were laid in different decomposition sites. Results showed that sediment burials showed significant influence on the decomposition rate of P. australis, in the order of S₁₀ (0.001990 day^?1)?≈?S₂₀ (0.001710 day^?1)?>?S₀ (0.000768 day^?1) (p?<?0.05). The macro and microelement in decomposing litters of the three burial depths exhibited different temporal variations except for Cu, Zn, and Ni. No significant differences in C, N, Pb, Cr, Zn, and Mn concentrations were observed among the three burial treatments except for Cu and Ni (p?>?0.05). With increasing burial depth, N, Cr, Cu, Ni, and Mn concentrations generally increased, while C, Pb, and Zn concentrations varied insignificantly. Sediment burial was favorable for C and N release from P. australis, and, with increasing burial depth, the C release from litter significantly increased, and the N in litter shifted from accumulation to release. With a few exceptions, Pb, Cr, Zn, and Mn stocks in P. australis in the three treatments evidenced the export of metals from litter to environment, and, with increasing burial depth, the export amounts increased greatly. Stocks of Cu and Ni in P. australis in the S₁₀ and S₂₀ treatments were generally positive, evidencing incorporation of the two metals in most sampling times. Except for Ni, the variations of C, N, Pb, Cr, Cu, Zn, and Mn stocks in P. australis in the S₁₀ and S₂₀ treatments were approximated, indicating that the strong burial episodes (S₂₀) occurred in P. australis marsh in the future would have little influence on the stocks of these elements. With increasing burial depths, the P. australis was particularly efficient in binding Cu and Ni and releasing C, N, Pb, Cr, Zn, and Mn, implying that the potential eco-toxic risk of Pb, Cr, Zn, and Mn exposure might be very serious. This study emphasized the effects of different burials on nutrient and metal cycling and mass balance in the P. australis marsh of the Yellow River estuary.     

Organic carbon,total nitrogen,and water-soluble ions in clouds from a tropical montane cloud forest in Puerto Rico

Chemical characterization to determine the organic and nitrogen fractions was performed on cloud water samples collected in a mountaintop site in Puerto Rico. Cloud water samples showed average concentrations of 1.09 mg L^?1 of total organic carbon (TOC), of 0.85 mg L^?1 for dissolved organic carbon (DOC) and of and 1.25 mg L^?1 for total nitrogen (TN). Concentrations of organic nitrogen (ON) changed with the origin of the air mass. Changes in their concentrations were observed during periods under the influence of African dust (AD). The ON/TN ratios were 0.26 for the clean and 0.35 for the AD periods. Average concentrations of all these species were similar to those found in remote environments with no anthropogenic contribution. In the AD period, for cloud water the concentrations of TOC were 4 times higher and TN were 3 times higher than during periods of clean air masses associated with the trade winds. These results suggest that a significant fraction of TOC and TN in cloud and rainwater is associated to airborne particulate matter present in dust. Functional groups were identified using proton nuclear magnetic resonance (¹H NMR) spectroscopy. This characterization led to the conclusion that water-soluble organic compounds in these samples are mainly aliphatic oxygenated compounds, with a small amount of aromatics. The ion chromatography results showed that the ionic species were predominantly of marine origin, for air masses with and without African dust influence, with cloud water concentrations of NO₃^? and NH₄⁺ much lower than from polluted areas in the US. An increase of such species as SO₄^2?, Cl^?, Mg²⁺, K⁺ and Ca²⁺ was seen when air masses originated from northwest Africa. The changes in the chemical composition and physical properties of clouds associated with these different types of aerosol particles could affect on cloud formation and processes.     

Influence of flooding and metal immobilising soil amendments on availability of metals for willows and earthworms in calcareous dredged sediment-derived soils

Soil amendments previously shown to be effective in reducing metal bioavailability and/or mobility in calcareous metal-polluted soils were tested on a calcareous dredged sediment-derived soil with 26 mg Cd/kg dry soil, 2200 mg Cr/kg dry soil, 220 mg Pb/kg dry soil, and 3000 mg Zn/kg dry soil. The amendments were 5% modified aluminosilicate (AS), 10% w/w lignin, 1% w/w diammonium phosphate (DAP, (NH₄)₂HPO₄), 1% w/w MnO, and 5% w/w CaSO₄. In an additional treatment, the contaminated soil was submerged. Endpoints were metal uptake in Salix cinerea and Lumbricus terrestris, and effect on oxidation-reduction potential (ORP) in submerged soils. Results illustrated that the selected soil amendments were not effective in reducing ecological risk to vegetation or soil inhabiting invertebrates, as metal uptake in willows and earthworms did not significantly decrease following their application. Flooding the polluted soil resulted in metal uptake in S. cinerea comparable with concentrations for an uncontaminated soil.