Green liquor dregs as an alternative neutralizing agent at a pulp mill

Green liquor dregs is the biggest waste fraction at sulphate pulp mills. It is commonly landfilled. Here we demonstrate that the utilization of green liquor dregs as a neutralizing agent for acidic wastewaters is a potential alternative and an environmentally friendly method in contrast to its landfill disposal. The liming effect value of 39.6% for green liquor dregs, expressed as Ca equivalent, is similar to the liming effect value of 38% of a commercial limestone product. In addition, the pH value of 10.7 indicates a strong liming effect.     

Ligand-less in situ surfactant-based solid phase extraction for preconcentration of silver from natural water samples prior to its determination by atomic absorption spectroscopy

A simple and rapid ligand-less in situ surfactant-based solid phase extraction method for preconcentration of silver from water samples is developed. In this method, a cationic surfactant containing a proper alkyl group (n-dodecyltrimethylammonium bromide) is dissolved in the aqueous sample and then a proper ion-pairing agent (ClO₄^?) is added. Due to the interaction between surfactant and ion-pairing agent, solid particles are formed and used for adsorption of silver carbonate. After centrifugation, the sediment is dissolved in 2.0 mL 1 M HNO₃ in ethanol and then aspirated directly into the flame atomic absorption spectrometer. Variables affecting the extraction efficiencies such as pH, concentrations of surfactant and CO₃^2?, ion pair concentration, and extraction time, are optimized. Under such conditions, the calibration curve is linear from 3 to 700 μg L^?1. Detection limit is 1.1 μg L^?1 with an enrichment factor of 37. The relative standard deviation for eight replicate measurements of 100 μg L^?1 is 2.1%. The method has been applied for the determination of silver in water samples.     

Determination of cobalt by air-assisted liquid–liquid microextraction

Abstract

A rapid and selective technique for extraction, preconcentration and determination of trace amounts of cobalt in water and pharmaceutical samples by air-assisted liquid–liquid microextraction combined with flame atomic absorption spectrometry is proposed. 1-Nitroso-2-naphthol is used as a complexing agent and 1-octanol as an extraction solvent. Parameters relevant for analytical effectivity, i.e. pH of sample solution, concentration of complexing agent, volume of extraction solvent, and number of extraction cycles are optimized using a Box–Behnken design. At optimum conditions, a dynamic linear range of 5–600?µg L^?1 is obtained, with a limit of detection of 1.2?µg L^?1. The method is used for determination of Co(II) in environmental water and pharmaceutical samples.     

Chemical Tracking and Marine Environmental Impact of Ocean Disposal of Calcium Carbonate Residue in the North Yellow Sea

The objective of this study is to determine the sedimentation rate and dispersion area of calcium carbonate residue dumped at sea and the impact to marine environment of dumping by a laboratory simulation experiment; chemical tracking in the field with the help of acoustic and optical tracking; and a comparative study of baseline conditions and marine environmental impact after dumping. Turbidity, pH and phosphate are selected as the chemical tracers to be monitored.

Results show that in the dumping area of 15 square miles with water depth of 50 m, if 217 t calcium carbonate residue is dumped (spot dumping) in the presence of a pycnocline with a current velocity of 60 cm/s (close to the maximum) the maximum dispersion distance of the calcium carbonate residue plume front is less than 2100 m; the dispersion area is less than 0.56 km²; and the maximum dispersion time is about 60 min when the turbidity and pH in the whole dispersion area return to background level. Therefore, the ocean disposal of calcium carbonate residue is feasible.     

Optimal control of lake pH for mercury bioaccumulation control

Mercury is recognized internationally as an important pollutant since mercury and its compounds are persistent, bioaccumulative and toxic, and pose human and ecosystem risks. A critical aspect of mercury cycling is its bioaccumulation, mainly as methylmercury, along the aquatic food web resulting in high risk of human exposure through contaminated fish consumption. Since lake acidity (pH) and mercury methylation are correlated, control of lake pH through lake liming is a possible option to mitigate mercury bioaccumulation. This work proposes to use optimal control theory to derive time-dependent lake liming strategies for a tighter control of lake pH. Since the behavior of the freshwater ecosystems such as lakes is often associated with considerable uncertainties, a robust and realistic analysis should incorporate such uncertainties. This work models the time-dependent uncertain variations in the basic lake pH value and derives the liming profiles in the presence of such seasonal pH fluctuations. Established techniques from real options theory are employed for modeling the uncertainty as a stochastic process, and stochastic optimal control is used for deriving liming profiles. The approach is critically evaluated through applications to various case study lakes. Considering the substantial costs associated with liming operations, the work formulates a multi-objective problem highlighting the tradeoff between accurate pH control and liming cost. The results of the control problem solution are also compared with heuristics based liming. The results, while highlighting the success of using time-dependent liming, put forth certain interesting aspects that might be helpful to a decision maker. The analysis is expected to make liming operation more reliable, thereby presenting one more tool to manage the harmful effects of mercury pollution.     

Influence of some coral reef communities on the calcium carbonate budget of Tiahura reef (Moorea,French Polynesia)

The calcium carbonate budget of coral reefs is the result of the interaction of the processes of calcification and biological degradation, and is reflected in the chemical properties of the seawater overlying the reefs. A series of experiments at Moorea Island (French Polynesia) in 1988 monitored the diurnal and nocturnal variations in the chemical properties of seawater under field and laboratory conditions. Our results revealed that in the study area (Tiahura barrier reef flat), the calcium carbonate budget varied over space and time as a function of location in the water current. Two in-situ sites were investigated; one was situated 100 m from the algal crest of the barrier reef, the other 300 m further downstream. As a result of cumulative upstream events, the daily net calcification was ten times higher at the downstream (5.22 gm^-2 d^-1) than at the upstream (0.45 gm^-2 d^-1) site. The carbonate uptake by in situ Porites lobata in enclosures (8 kgm^-2 yr^-1) was ten times higher than the uptake by the whole community in the surrounding water (0.8 kgm^-2 yr^-1) and five times higher than that recorded for P. lobata in laboratory experiments (1.4 kgm^-2 yr^-1), where illumination levels were 10% of in situ levels. In laboratory experiments, the planktonic fraction of the seawater had no perceptible influence on the calcium carbonate budget. In the absence of bioeroders, living coral totally depleted the carbonate content of the seawater (3.7 gm^-2d^-1). Bioerosive organisms played an important role in restoring this calcium carbonate; e.g. sea urchins grazing on algal turf covering dead coral ingested CaCO₃ and released this as a carbonate powder (1.26 gm^-2d^-1); a form of carbonate which is extremely accessible to chemical dissolution.     

Ultrasound-assisted emulsification/microextraction based on solidification of trace amounts of thallium prior to graphite furnace atomic absorption spectrometry determination

In the present work, determination of ultratrace amounts of thallium in water samples was performed by ultrasound-assisted emulsification microextraction based on solidification of a floating organic drop as sample preparation method prior to furnace atomic absorption spectrometry. 1-(2-Pyridylazo)-2-naphthol was used as chelating agent. The factors influencing the complex formation and extraction, such as pH of the aqueous solution, the type and the volume of extraction solvent, the volume of chelating agent solution, and the extraction time were investigated. Under optimized conditions, the enrichment factor was 200. The calibration graph was linear from 0.2 to 10.0 μg L^?1 with a correlation coefficient of 0.9966, the detection limit was 0.03 μg L^?1 and reproducibility was ±3.3% (C = 5.0 μg L^?1, n = 8). The method was successfully applied for the determination of thallium in water samples.     

Application of eggshell waste for the immobilization of cadmium and lead in a contaminated soil

Liming materials have been used to immobilize heavy metals in contaminated soils. However, no studies have evaluated the use of eggshell waste as a source of calcium carbonate (CaCO₃) to immobilize both cadmium (Cd) and lead (Pb) in soils. This study was conducted to evaluate the effectiveness of eggshell waste on the immobilization of Cd and Pb and to determine the metal availability following various single extraction techniques. Incubation experiments were conducted by mixing 0–5% powdered eggshell waste and curing the soil (1,246 mg Pb kg^?1 soil and 17 mg Cd kg^?1 soil) for 30 days. Five extractants, 0.01 M calcium chloride (CaCl₂), 1 M CaCl₂, 0.1 M hydrochloric acid (HCl), 0.43 M acetic acid (CH₃COOH), and 0.05 M ethylendiaminetetraacetic acid (EDTA), were used to determine the extractability of Cd and Pb following treatments with CaCO₃ and eggshell waste. Generally, the extractability of Cd and Pb in the soils decreased in response to treatments with CaCO₃ and eggshell waste, regardless of extractant. Using CaCl₂ extraction, the lowest Cd concentration was achieved upon both CaCO₃ and eggshell waste treatments, while the lowest Pb concentration was observed using HCl extraction. The highest amount of immobilized Cd and Pb was extracted by CH₃COOH or EDTA in soils treated with CaCO₃ and eggshell waste, indicating that remobilization of Cd and Pb may occur under acidic conditions. Based on the findings obtained, eggshell waste can be used as an alternative to CaCO₃ for the immobilization of heavy metals in soils.     

Hair burning and liming in tanneries is a source of pollution by arsenic,lead, zinc,manganese and iron

Heavy metals in the environment may be toxic for human and animals. Tanneries are a source of pollution by heavy metals. There is little information on heavy metals pollution in tanneries, especially on metals produced by the process of hair burning and liming. Liming is the first stage of chemical treatment where animal hair or wool is removed with sodium sulphide and calcium oxide. Here we studied cow, goat, buffalo and sheep hair, conventional liming agents and liming wastewaters from several sources. Samples were acid-digested and aliquots were analysed by atomic absorption spectroscopy following APHA standard method to measure concentrations of arsenic, lead, cadmium, zinc, manganese and iron. Results show that the range of metal contents in hair or wool and liming agents are 1.3–8.2 mg/kg for arsenic, 0.02–21.8 mg/kg for lead, 17.7–121.0 mg/kg for manganese, 7.3–141.1 mg/kg for zinc and 119.6–10613.8 mg/kg for iron. Liming wastewaters contain 1.9–5.6 µg/L arsenic, 0.03–6.05 µg/L lead, 38.6–139.0 µg/L manganese, 144.0–171.5 µg/L zinc and 399.5–1069.0 µg/L iron. Cadmium was below detection limits. This is the first investigation that reveals that hair burning liming operation is a potential source of heavy metals in the environment.     

Chemical Tracking and Marine Environmental Impact of Ocean Disposal of Calcium Carbonate Residue in the North Yellow Sea

The objective of this study is to determine the sedimentation rate and dispersion area of calcium carbonate residue dumped at sea and the impact to marine environment of dumping by a laboratory simulation experiment; chemical tracking in the field with the help of acoustic and optical tracking; and a comparative study of baseline conditions and marine environmental impact after dumping. Turbidity, pH and phosphate are selected as the chemical tracers to be monitored.

Results show that in the dumping area of 15 square miles with water depth of 50 m, if 217 t calcium carbonate residue is dumped (spot dumping) in the presence of a pycnocline with a current velocity of 60 cm/s (close to the maximum) the maximum dispersion distance of the calcium carbonate residue plume front is less than 2100 m; the dispersion area is less than 0.56 km²; and the maximum dispersion time is about 60 min when the turbidity and pH in the whole dispersion area return to background level. Therefore, the ocean disposal of calcium carbonate residue is feasible.     

二(2-乙基己基)磷酸络合萃取邻氨基苯酚的研究

以二(2-乙基己基)磷酸(D2EHPA)为萃取剂,研究稀释剂种类、萃取剂浓度、溶液的初始pH值、溶液中甲(乙)醇等因素对邻氨基酚(OAP)稀溶液分配比(D)的影响.结果表明:溶液的初始pH值在7左右时,D有最大值;D值随二(2-乙基己基)磷酸浓度的增大而提高,且在极性环境要优于惰性环境;甲(乙)醇是影响萃取结果的主要因素.     

Long-term effects of short-term perturbation in a subalpine grassland

Theoretical advances and short-term experimental studies have furthered our understanding of how ecosystems respond to perturbation. However, there are few well-replicated experimental studies that allow an assessment of long-term responses. Results from a controlled, large-scale field experiment in a subalpine grassland near Interlaken, Switzerland, show that 2-4 years of liming (Ca: 40 g x m(-2) x yr(-1)) still significantly affected the composition of the vegetation and the soil microbial community nearly 70 years after the treatments were imposed, whereas NPK fertilization (8 g x m(-2) x yr(-1)) only marginally affected vegetation composition. The exchangeable content of Ca ions and soil pH were higher in limed plots but were unaffected in fertilized plots. Plant species and PLFAs (phospholipid fatty acids) indicating low pH values were found in higher abundance in the unlimed plots, suggesting that the long-lasting effects of liming on the above- and belowground communities were mediated through changes in soil pH. The results of this long-term study indicate that the resilience of mountain ecosystems may be particularly low in response to perturbations that substantially alter soil pH or other key determinants of belowground processes.     

Determination of traces of fluorine,chlorine, bromine,cadmium and lead in plastic materials

This paper describes the quantitative determination of F, Cl, Br, Cd and Pb in plastic materials. The concentration of the elements Cl, Br, Cd and Pb is first semiquantitatively measured by X‐ray fluorescence spectrometry (XRF) directly in the solid sample with a detection limit of approximately 10 μg/g. Afterwards, F and any of the other elements which exceed the limit values for materials which are disposable without special precautions are measured after the digestion of the material. The samples are digested either under pressure in an oxygen atmosphere for F, Cl and Br or under pressure with nitric acid for Cd and Pb. The digestion converts the halides to the anions which are measured potentiometrically (F^‐, Br^‐) or with ion chromatography (Cl^‐). Cd and Pb are measured by graphite furnace atomic absorption spectrometry (GF‐AAS). The determination limits achieved are 20 μg/g for F and Br, 250 μg/g for Cl, 0.01 μg/g for Cd and 0.2 μg/g for Pb, all below the limit values set by current regulations in Switzerland.     

An alternative method to measure carbonate in soils by FT-IR spectroscopy

Measurements of calcium carbonate contents in soils were performed with FT-IR (Fourier transform infrared) spectroscopy and with the gas volumetric Scheibler method. To the authors’ knowledge it is the first time that carbonate was quantified in soil samples by FT-IR spectroscopy. The carbonate contents of the test soils ranged from 11.3 to 13.1%. Both methods gave similar results, however, results obtained from FT-IR spectra depend on the spectral band used for the carbonate determination. In our investigation we used the bands at 875 and 2506 cm⁻¹. In case of the band at 2506 cm⁻¹ the difference between FT-IR and Scheibler method was a factor of 1.56, in case of 875 cm⁻¹ the respective factor was 1.16. It can be concluded that FT-IR with both bands has a potential to be used in practice as substitution of the Scheibler method. The advantages of the FT-IR method are better reproducibility and the simultaneous characterization of soil organic matter in bulk samples. The disadvantage is its higher cost.     

施用石灰对酸性土壤中氧化亚氮形成的影响

对酸性红壤施用石灰和N2O生成之间的关系进行了探讨。结果表明,在好气条件下,石灰的施用与NH4＋氧化过程中N2O的产生量之间的关系不明显。但随着石灰施用量的增加,厌气条件下NO3－还原过程中N2O的积累量明显增加了,这与施用石灰后土壤pH升高而提高了硝酸还原酶活性有关。试验还表明,尽管在厌气条件下土壤pH较高有利于NO3－还原成NO2－,但当缺乏有效碳源时,NO2－向N2O的进一步还原受到限制,易发生NO2－的积累。     

Effect of wastewater composition on the calcium carbonate precipitation in upflow anaerobic sludge blanket reactors

Calcium carbonate often precipitates in anaerobic reactors treating wastewater with high calcium content. The aim of this paper is to study the effect of wastewater composition on calcium carbonate precipitation in upflow anaerobic sludge blanket (UASB) reactors. Two laboratory-scale UASB reactors were operated with calcium-containing influents using acetate and carbohydrate as substrate, respectively. There was an obvious accumulation of inorganic precipitate observed in the biogranules. Observations via scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) showed that the acclimated biogranules in the two reactors differed in microstructure. Calcium carbonate was found to have precipitated on the surface of acetate-degrading biogranules, but precipitated at the core of the carbohydrate-degrading biogranules. The results indicated that substrates had significant influence on the location of calcium carbonate precipitation in anaerobic granular sludge, which was expected due to the different methanogens distribution and pH gradient within the granular sludge degrading various substrates. Moreover, the location of calcium carbonate precipitation substantially affected the specific methanogenic activity (SMA) of the granular sludge. The SMA of the acetate-degrading biogranules dropped from \(1.96 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} \) to \(0.61 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} \) after 180-d of operation in the reactor. However, the SMA of the carbohydrate-degrading biogranules was not adversely affected by calcium carbonate precipitation.     

Terrestrial liming benefits birds in an acidified forest in the northeast

Studies in Europe have reported negative effects of acid deposition on forest birds, and research in North America has identified links between forest bird abundance and rates of acid deposition. We examined the bird community in an acidified forest in central Pennsylvania (USA) and evaluated the effects of terrestrial lime application on birds. We used a before-after control-impact (BACI) study design, with one year of observation before (2003) and three years after lime application (2004, 2005, and 2006). Between the 2003 and 2004 field seasons, 4500 kg/ha of dolomitic lime were applied to two of four 100-ha watersheds. Each year, we monitored bird abundance and Ovenbird (Seiurus aurocapilla) eggshell thickness and territory size. Soil and snail abundance data were also collected. The bird community and territory size results indicated that the study area may be providing low-quality habitat for forest birds, perhaps as a result of acid deposition. We found lower forest bird abundances than have been found in less acidified areas of Pennsylvania, and larger Ovenbird territory sizes than have been found in other studies. We found a significant positive relationship between soil calcium and bird abundance, indicating that soil calcium may affect bird abundance. Liming increased soil calcium and pH and led to increased snail and bird abundances. After liming, bird abundance was positively related to snail abundance. No significant changes occurred in Ovenbird territory size or eggshell thickness. Our results suggest that acid deposition could be responsible for reduced bird abundance, and that liming is a potential mitigation technique.     

Construction of carbon nanotube-based microcapsules by self-assembly

Carbon nanotubes possess unique structures and outstanding properties. However, dispersion and manipulation of carbon nanotubes in solvents severely limit their application. A solution is building carbon nanotube-based microcapsules that combine both the properties of carbon nanotubes and capsules. Carbon nanotube-based microcapsules have indeed great potential applications including catalysts, adsorbents, and controlled-release materials. Here, we built carbon nanotube-based microcapsules by electrostatic self-assembly to develop novel composite materials. The construction and morphology of microcapsules were characterized by Raman spectroscopy, infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. Pre-films composed of poly(sodium 4-styrenesulfonate) and poly(diallyldimethylammoinum chloride) were assembled onto calcium carbonate (CaCO₃) microparticles to construct positive solid templates. The carboxylated carbon nanotubes were then successfully assembled on the CaCO₃ template using a self-assembly technique. Ethylene diamine tetraacetic acid (EDTA) was used as a powerful chelating agent to remove the CaCO₃ cores by chelation between EDTA and calcium, thus completing the construction of carbon nanotube-based hollow microcapsules. The spherical shapes of the microcapsules were well retained, and the carbon nanotubes were anchored evenly in the polyelectrolyte layers.     

The Brown Trout Population at Loch Fleet Eight Years After Liming

Abstract

At the start of the Loch Fleet Project in 1984, the Loch and the upper 7 km of its efferent stream were found to be devoid of trout (Salmo trutta) as a result of acidification. Following the liming treatments applied to the catchment, from 1986 the formerly toxic water quality conditions (pH ～ 4.5, calcium ～ 1 mgl^?1, elevated aluminium and heavy metal levels) were eliminated, and trout were reintroduced on two occasions, in 1987 and 1988. A total of 520 fish were stocked, at a combined density equivalent to 5.5 kg ha^?1. Surveys of the loch and stream populations were carried out annually until 1993 to monitor their development, using a range of techniques, including electrofishing, gill-netting, seine-netting, spawner trapping and mark-release recapture methods. Length and scale- analysis were used to investigate fish growth.

The trout population in Loch Fleet expanded rapidly as a result of natural spawning in the loch's main feeder stream, augmented by the use of an artificial spawning bed which was constructed at the loch outlet in 1990. in mid-1983 the stock density, estimated by mark-recapture census methods, had increased to 24.9 kg ha^?1. Poor recruitment in the years 1991–93, however, reduced the rate of expansion and resulted in a population comprising mainly older individuals. the poor recruitment in these years was not fully explained but was not caused by water quality and was most likely a result of fry washout by spring spates.

Fish growth rates were high initially and were estimated on the basis of the Elliott trout growth model to be optimal for the prevailing water temperature regime of the loch. By 1991, growth rates had fallen, probably as a result of competition for food, but showed signs of recovery towards the end of the study period in 1993, following the period of lower population densities of young fish.

Trout rapidly repopulated the loch's outlet stream after 1987 but have remained sparse and have shown no signs of spawning within most of the stream. Water analyses have shown that the liming of the Loch Fleet catchment has minimal impact on downstream waters when flows are high, so that potentially toxic acid episodes have not been prevented.     

Application of eggshell waste for the immobilization of cadmium and lead in a contaminated soil

Liming materials have been used to immobilize heavy metals in contaminated soils. However, no studies have evaluated the use of eggshell waste as a source of calcium carbonate (CaCO?) to immobilize both cadmium (Cd) and lead (Pb) in soils. This study was conducted to evaluate the effectiveness of eggshell waste on the immobilization of Cd and Pb and to determine the metal availability following various single extraction techniques. Incubation experiments were conducted by mixing 0-5% powdered eggshell waste and curing the soil (1,246 mg Pb kg?1 soil and 17 mg Cd kg?1 soil) for 30 days. Five extractants, 0.01 M calcium chloride (CaCl?), 1 M CaCl?, 0.1 M hydrochloric acid (HCl), 0.43 M acetic acid (CH?COOH), and 0.05 M ethylendiaminetetraacetic acid (EDTA), were used to determine the extractability of Cd and Pb following treatments with CaCO? and eggshell waste. Generally, the extractability of Cd and Pb in the soils decreased in response to treatments with CaCO? and eggshell waste, regardless of extractant. Using CaCl? extraction, the lowest Cd concentration was achieved upon both CaCO? and eggshell waste treatments, while the lowest Pb concentration was observed using HCl extraction. The highest amount of immobilized Cd and Pb was extracted by CH?COOH or EDTA in soils treated with CaCO? and eggshell waste, indicating that remobilization of Cd and Pb may occur under acidic conditions. Based on the findings obtained, eggshell waste can be used as an alternative to CaCO? for the immobilization of heavy metals in soils.