Optimisation of bisphenol A removal from water using chemically modified pine bark and almond shell

The ability of pine bark and almond shells to remove bisphenol A (BPA) from aqueous solutions was evaluated. Samples of these traditional agro-forestry by-products were milled, sieved into different particle size fractions (0.10–0.15 and 1.5–2.0 mm) and submitted to two different types of treatment. Sorption experiments were conducted in a batch system at room temperature and natural pH. Sorption equilibrium was attained after 48 h for all systems under study. Bisphenol A was adsorbed more effectively on the smaller particles of the sorbents. Pine bark and almond shell pretreated with formaldehyde presented higher sorption efficiency (95%), followed by almond shell (87%) and pine bark (82%) washed with hot water. All the sorption isotherms were found to fit a Freundlich equation, with correlation coefficients (R ²) between 0.823 and 0.989. The sorption coefficient (K _F) ranged from 0.06 to 0.74 (mg^1?1/n ·L ^1/n ·g ^?1). These results indicate that utilisation of both materials as an alternative sorbent for the removal of bisphenol A from contaminated waters is promising because they are available in large amounts and have an acceptable cost–efficiency ratio when compared with traditional adsorbents.     

The sorption of selenite from aqueous solutions by pyrite

Selenium (Se) is an essential trace nutrient for mammals; however, the range between deficit and toxic levels is narrow. In this study, the potential sorption of selenite onto pyrite particles from an aqueous solution was investigated. An intraparticle diffusion model was used to describe kinetic data of sorption, yielding diffusivity values of 5 × 10^?7 cm²/s. The Langmuir isotherm equation could be used to describe the experimental data. The fitting results indicated that b and {Se(IV)}_max have values of 0.37 L/mg and 3.49 mg/g, respectively. The sorption of selenite onto the surface of pyrite particles was dependent on a pH range of 2–12, and the quantity of sorption onto pyrite was negatively correlated with pH; that is, the amount of sorption onto pyrite increased with a decrease in pH. In addition, organic matter did not exert a significant effect on removal of selenite. With a reaction time greater than 1 week, sorption of selenite onto pyrite particles was found to partially reduce the amount of elemental Se.     

Adsorption and partition of benzo(a)pyrene on sediments with different particle sizes from the Yellow River

Experiments have been carried out to study the sorption of Benzo(a)pyrene(Bap) on sediment particles from the Yellow River using a batch equilibration technique. Effects of particle size on the adsorption and partition of Bap were investigated with the particle content of 3 g/L. Several significant results were obtained from the study. (1) Isotherms of Bap could be fitted with the dual adsorption-partition model under different particle sizes, and the measured value of the adsorption and partition was in agreement with the theoretical value of the dual adsorption-partition model. (2) When the particle diameter was d ? 0.025 mm, the adsorption was predominant in the sorption of Bap, which accounted for 68.7%–82.4% of the sorption. For the particles with the size of 0.007 mm?d<0.025 mm, the adsorption was predominant when the equilibrium concentration of Bap was 0–8.87 μg/L in the water phase; and the partition was predominant when the equilibrium concentration of Bap was higher than 8.87 μg/L in the water phase. When the particle diameter was d<0.007 mm, the partition was predominant. (3) On the point of particle size, the contribution of adsorption to sorption followed the order: “d?0.025 mm”>“0.007 mm ?d<0.025 mm” >“d<0.007 mm”. (4) The partition coefficients of Bap in solids with different particle sizes were linearly correlated with the organic content, and the K _oc of Bap was about 1.26 × 10⁵ (L/kg).     

Removal of arsenic (V) from aqueous medium using manganese oxide coated lignocellulose/silica adsorbents

Arsenic (V) adsorption on manganese oxide coated rice wastes was investigated in this study. The modified adsorbents were characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy, and pH measurements to determine the point of zero charge. Batch adsorption equilibrium experiments were conducted to study the effects of pH, contact time, and initial concentration on arsenic removal efficiency. The adsorption capacity of rice waste was significantly improved after modification with permanganate. The Langmuir isotherm model fitted the equilibrium data better than the Freundlich model which confirms surface homogeneity of the adsorbent. Maxima adsorption capacities are determined as 10 and 12 mg/g at pH 3 for manganese oxide coated rice husk and straw, respectively. The adsorption energy indicates that the adsorption process may be dominated by chemisorption. Pseudo-second-order rate equation described the kinetics sorption of arsenic with good correlation coefficients, better than a pseudo-first-order equation. Manganese oxide coated rice husk and straw appear to be promising low cost adsorbents for removing arsenic from water.     

Selective sorption of perfluorooctane sulfonate on molecularly imprinted polymer adsorbents

Perfluorooctane sulfonate (PFOS), as a potential persistent organic pollutant, has been widely detected in water environments, and has become a great concern in recent years. PFOS is very stable and difficult to decompose using conventional techniques. Sorption may be an attractive method to remove it from water. In this study, the molecularly imprinted polymer (MIP) adsorbents were prepared through the polymerization of 4-vinylpyridine under different preparation conditions in order to remove perfluorooctane sulfonate (PFOS) from water. The MIP adsorbents using perfluorooctanoic acid (PFOA) as the template had good imprinting effects and could selectively remove PFOS from aqueous solution. The sorption behaviors including sorption kinetics, isotherms, and effect of pH, salt, and competitive anions were investigated. Experimental results showed that the sorption of PFOS on the MIP adsorbents was very fast, pH-dependent, and highly selective. The achieved fast sorption equilibrium within 1 h was attributed to the surface sorption on the fine adsorbents. The sorption isotherms showed that the sorption selectivity of PFOS on the MIP adsorbents decreased at high PFOS concentrations, which may be due to the double-layer sorption and the formation of PFOS micelles on the sorbent surface. The sorption of PFOS on the MIP adsorbents was mainly dominated by the electrostatic interaction between the protonated vinylpyridine on the adsorbent surface and the anionic PFOS. The prepared MIP adsorbents can potentially be applied in water and wastewater treatment for selective removal of PFOS.     

雄烯二酮在我国典型土壤中的吸附特性

采用批吸附室内模拟实验研究了雄烯二酮在我国红壤、潮土、黑土3种典型土壤中的吸附特征,以及牛粪溶解态有机质(DOM)对土壤吸附雄烯二酮的影响。结果表明,雄烯二酮在土壤中吸附动力学符合Elovch方程(R20.89),热力学特征可通过Freundlich等温吸附方程(R20.83)描述,土壤对雄烯二酮的吸附呈非线性吸附特征,其中潮土吸附等温线的非线性最强(n=0.37);吸附系数K f介于6.0~20.2,并与有机质含量呈显著正相关(p0.05)。雄烯二酮浓度较低时,共存牛粪DOM抑制其在土壤表面的吸附作用。研究认为,有机质是土壤吸附雄烯二酮的主要组分,共存牛粪DOM可促进雄烯二酮向地表水和地下水的迁移。     

Vertical infiltration of fuel oil hydrocarbons in an agricultural soil

The influence of rainfall, air temperature and soil moisture on the vertical mobility in the soil of fuel oil hydrocarbons (HC) was investigated in a field experiment. A controlled spreading of fuel oil (nC10‐nC25) was performed at a rate of 5 L HCm^‐2 on an agricultural soil in summer and in winter. Concentration, chemical composition of HC and soil moisture were regularly determined at different soil depths between 0 and 140 cm, 1 h, 3, 8and 15 days (d) after the spreading of oil. Sorption of hydrocarbons onto the organo‐mineral matrix of the soil was studied in laboratory experiments. The results showed that in summer, with an air temperature of 24°C and without water leaching in the soil profile, 65% of the initial HC remained trapped in the 0–140 cm soil layer, about 20% of the HC volatilized and around 15% migrated deeper. A vertical selective migration of the lightest (nC10‐nC15) HC (naphthas) was shown lSd after the spreading of fuel oil. Naphthas progressively reached the 120–140 cm soil layers whereas the heavy fractions of oil (nC17‐nC25) migrated and concentrated in the 0–60 cm soil layers. In winter, when soil was regularly watered by rainfalls and at low air temperatures, only 47% of the initial HC remained in the 0–140 cm profile after 15 d. A fast vertical infiltration of naphthas occurred within the first 3 d. After 15 d, all HC were detected in the same relative amounts as in the initial oil in the whole profile. Volatilization was negligible in winter and an increase in the migration of total oil at depth in the soil profile was shown. As inferred from the laboratory experiments, the high soil moisture led to the decrease in HC sorption on the organo‐mineral matter of the soil.     

Oil exposure in a warmer Arctic: potential impacts on key zooplankton species

Oil exploration activities are rapidly increasing in Arctic marine areas with potentially higher risks of oil spills to the environment. Water temperatures in Arctic marine areas are simultaneously increasing as a result of global warming. Potential effects of a combination of increased water temperature and exposure to the PAH pyrene were investigated on fecal pellet and, egg production and hatching success of two copepod species, Calanus finmarchicus and Calanus glacialis, sampled in Disko Bay, Greenland on 23–25 April 2008. The two species were exposed daily to nominal pyrene concentrations of 0-0.01-0.1-1-10-100 nM at water temperatures of 0.5, 5 and 8°C for 9 and 7 days, respectively. Daily measurements of faecal pellet production, egg production and hatching showed different responses of the two species to the applied stressors. When temperature increased, low concentrations of pyrene caused a decrease in faecal pellet production by C. finmarchicus, whereas C. glacialis faecal pellet production showed no negative response to pyrene exposure when temperatures increased. Pyrene exposure decreased egg production of C. finmarchicus at all temperatures, but the species was more sensitive at 0.5 and 8°C. A lag period of 1 day before egg production began was prolonged with several days when warmer water was combined with pyrene exposure. Egg production by C. glacialis was only negatively affected by pyrene in a dose-dependent manner at 0.5°C. Hatching success in both species was not affected by pyrene, where increased water temperatures led to a higher hatching success. In conclusion, C. glacialis seemed to be the less sensitive of the two species to the stress combination of increased water temperature and pyrene exposure. As a consequence of the differential responses of the two species, their competition can be impaired with a consequent impact on energy transfer between trophic levels.     

Assessment of Groundwater Quality and Contamination from Uranium-Bearing Black Shale in Goesan–Boeun Areas, Korea

This study was initiated to identify the impact of metals and uranium enriched soil and black shale in groundwater quality and contamination. From a Piper diagram, groundwater was classified into four types as (Ca+Mg)–HCO₃ type, (Ca+Mg)–SO₄ type, the mixed type of these two and Na–HCO₃ type, reflecting the complicated nature of geology of the study area. Silicate weathering appeared to be the major water–rock interaction. In groundwater, metals including Cr, Pb, Cu and V, previously identified as being enriched in soils and black shale, were much lower in concentrations than Korean and US EPA drinking water guidelines. Instead, Fe and Mn caused major water-quality problems. In the artesian groundwater from an abandoned uranium mine, the uranium concentration was 21.3 µg L^–1, slightly higher than EPA guidelines of 20 µg L^–1. Heavy metals in groundwater appeared to be controlled mostly by sorptions on to Fe- and Mn-oxyhydroxides. They could be remobilised in groundwater with changes of pH and Eh conditions due to acid mine drainage from black shale or the recharge of fresh water. Uranium would be associated with carbonate and sulphate complexes in groundwater. Because of the remaining water-quality problems in the study area, we suggested containment of identified mine wastes, considering remedial measures for local problems with Fe and Mn, continuous monitoring of groundwater and developing groundwater from deep aquifers.     

Metal Interactions in carcinogenesis†

Mixed exposures to a number of metallic compounds may give rise to a carcinogenic response in humans.

An interaction between occupational exposure to arsenic and cigarette smoking has been documented epidemiologically. A multiplicative effect was indicated concerning the occurrence of lung cancer when both of the exposures were present. Several experimental studies have been reported in the literature concerning interactions between benzo(a)pyrene and Fe₂O₃ as well as some other metallic compounds like Ni₃S₂, PbO, MgO and TiO₂ in relation to respiratory carcinogenicity. There is also limited evidence of a positive interaction between arsenic trioxide and benzo(a)pyrene. Particles containing V and Ni were obtained from the flue gases of power plants burning heavy fuel oil. Such particles were not carcinogenic themselves but enhanced the carcinogenicity of benzo(a)pyrene even more efficiently than Fe₂O₃.

Increased dietary selenium intakes can decrease the carcinogenicity of several organic carcinogens in animals and dietary zinc can effectuate both enhancement and inhibition of carcinogenicity depending on dietary concentration.     

几类有机污染物的微塑料/水分配系数的线性溶解能关系模型

水体中的微塑料会吸附其中的有机污染物,影响有机污染物和微塑料的环境归趋和生态毒性。研究微塑料对有机污染物的吸附行为,对于评价有机污染物和微塑料的环境赋存、迁移及生物有效性有重要意义。污染物在微塑料与水之间的平衡分配系数(Kd),是表征微塑料对有机污染物吸附能力的重要参数。实验方法难以逐个测定众多有机污染物的Kd值,有必要发展其预测模型。本研究搜集了有机污染物的线性溶解能关系(LSER)参数及Kd值,构建了可预测有机污染物在聚丙烯微塑料与海水、聚乙烯微塑料与海水、聚乙烯微塑料与淡水之间Kd值的LSER模型。模型具有良好的拟合优度(R2adj介于0.794~0.903)、稳健性(Q2LOO和Q2BOOT分别介于0.763~0.863和0.720~0.804)和预测能力(R2ext和Q2ext分别介于0.886~0.971和0.825~0.954),能够用于预测多氯联苯、多环芳烃、六氯环已烷和氯苯类有机污染物的Kd值。     

Metal immobilization by sludge-derived biochar: roles of mineral oxides and carbonized organic compartment

Pyrolyzing sludge into biochar is a potentially promising recycling/disposal solution for municipal wastewater sludge, and the sludge-derived biochar (SDBC) presents an excellent sorbent for metal immobilization. As SDBC is composed of both mineral oxides and carbonized organic compartment, this study therefore compared the sorption behaviour of Pb and Zn on SDBC to those of individual and mixture of activated carbon (AC) and amorphous aluminium oxide (Al₂O₃). Batch experiments were conducted at 25 and 45 °C, and the metal-loaded sorbents were artificially aged in the atmosphere for 1–60 days followed by additional sorption experiments. The Pb sorption was generally higher than Zn sorption, and the co-presence of Pb reduced Zn sorption on each studied sorbent. Higher sorption capacities were observed at 45 °C than 25 °C for SDBC and AC, while the opposite was shown for Al₂O₃, indicating the significance of temperature-dependent diffusion processes in SDBC and AC. Nevertheless, metal sorption was more selective on Al₂O₃ that showed a greater affinity towards Pb over Zn under competition, correlating with the reducible fraction of sequential extraction. Furthermore, significant amounts of Pb and Zn were additionally sorbed on SDBC following 30-day ageing. The X-ray diffraction revealed the formation of metal-phosphate precipitates, while the X-ray photoelectron spectroscopy showed a larger quantity of metal–oxygen bonding after 30-day ageing of metal-loaded SDBC. The results may imply favourable long-term transformation and additional sorption capacity of SDBC. In conclusion, SDBC resembles the sorption characteristics of both organic and mineral sorbents in different aspects, presenting an appropriate material for metal immobilization during soil amendment.     

Chemically modified biochar produced from conocarpus waste increases NO<Subscript>3</Subscript> removal from aqueous solutions

Biochar has emerged as a universal sorbent for the removal of contaminants from water and soil. However, its efficiency is lower than that of commercially available sorbents. Engineering biochar by chemical modification may improve its sorption efficiency. In this study, conocarpus green waste was chemically modified with magnesium and iron oxides and then subjected to thermal pyrolysis to produce biochar. These chemically modified biochars were tested for NO₃ removal efficiency from aqueous solutions in batch sorption isothermal and kinetic experiments. The results revealed that MgO-biochar outperformed other biochars with a maximum NO₃ sorption capacity of 45.36 mmol kg^?1 predicted by the Langmuir sorption model. The kinetics data were well described by the Type 1 pseudo-second-order model, indicating chemisorption as the dominating mechanism of NO₃ sorption onto biochars. Greater efficiency of MgO-biochar was related to its high specific surface area (391.8 m² g^?1) and formation of strong ionic complexes with NO₃. At an initial pH of 2, more than 89 % NO₃ removal efficiency was observed for all of the biochars. We conclude that chemical modification can alter the surface chemistry of biochar, thereby leading to enhanced sorption capacity compared with simple biochar.     

Analytik von Mineralölkohlenwasserstoffen: Die Problematik der Probenaufbereitung

For the determination of mineral oil hydrocarbons in water and soil, IR-as well as GC/FID-methods (DEV H-18, ISO/TR 11046, NEN 5733) are used. Independent of the measurement method, different clean-up procedures are prescribed in these standard methods. Aluminium oxide, silica gel and magnesium silicate (Florisil^®) are used as adsorbents. This article describes the problems of clean-up occurring in mineral oil analysis using selected substances. Tests concerning the type of adsorbent, extract medium, clean-up-technique and extract/adsorbent-ratio are presented. It will be shown that the clean-up procedure has to be counted as a significant factor of influence in the determination of mineral oil hydrocarbons. The sources of errors resulting from clean-up as well as the possibilities to avoid them are presented. An extraction solvent for soils which is simple to handle and optimally adjustable to the requirements of the clean-up procedure is presented.     

Adsorptive removal of mercury from acid mine drainage: a comparison of silica and maghemite nanoparticles

Mercury adsorption by silica and maghemite nanoparticles (NPs) was studied with the aim of comparing their performance in the remediation of acid mine drainage (AMD) contaminated water. Calculated distribution coefficients (K_d) showed that both NPs are exceptional adsorbents. However, adsorbate coverage per unit area was 30 times higher for maghemite than for silica NPs, despite the latter having a surface area ～15 times greater. Maghemite adsorbed 75% of available Hg compared to 56% by silica, making it a more efficient sorbent than silica under AMD conditions. Kinetics and isotherm data for both adsorbents were fitted by the pseudo-second-order (R² = 1) and the Freundlich (R² ≥ 0.98) models, implying that adsorption to both NP types was by chemisorption. Adsorption increased with NP concentrations and pH and was enhanced in the presence of manganese and sulfate ions although adsorption to silica was inhibited in 1:2 Hg-to-Mn systems. Importantly, trends in simulated wastewater were replicated in actual AMD-contaminated water samples. This study highlights the fact that properties besides surface area and charge of adsorbents determine adsorbent performance, and superior attributes may not always lead to higher adsorption efficiencies.     

Removal of Cr(VI) from aqueous solutions by the culm of bamboo grass treated with concentrated sulfuric acid

We prepared a carbonaceous sorbent for Cr(VI) from the culm of Sasa kurilensis by dehydration with concentrated H₂SO₄. The removal of Cr(VI) by the sorbent was highly solution pH dependent and mainly governed by physicochemical sorption. The equilibrium data fit well in the Langmuir isotherm model and indicate the endothermic nature of the Cr(VI) sorption. The desorption experiments suggest that the Cr(VI) sorption is generally irreversible, owing to strong interaction of HCrO₄⁻ with the active sites of the sorbent.     

Regression models for some solute distribution equilibria in the terrestrial environment

Sorption coefficients (K_p) of several organochlorine insecticides (OCs) in volcanic ash silt from Central Java are presented.

Selected experimental and estimated octanol‐water partition coefficient (P) values are used to study log‐log regressions with K_p data collected from the literature (PAHs, chlorophenols, phenylureas, chloro‐s‐triazines, carbamates and organophosphorus insecticides) and those of the OCs determined in the present study. Leaching distances and bioactivities in soil are correlated with the K_p values of the pesticides, and with the organic matter and the water content of the soil.     

Calcium and magnesium carbonate concentrations in different growth regions of gorgonians

Four of the most abundant gorgonian species from the southwestern Cape waters, Eunicella papillosa (Esper, 1797), E. alba (Esper, 1797), E. tricoronata Velimirov, 1971 and Lophogorgia flamea (Ellis and Solander, 1786) were analysed for Ca and Mg by atomic absorption spectroscopy (AAS) and ethylenediaminetetraacetate (EDTA) titration. The total mineral content in the peripheral tissues, excluding the axial skeleton, expressed as the sum of CaCO₃ and MgCO₃ of dry matter was between 65.5 and 83.5%. The mineral content varied in different growth regions and all specimens showed a higher degree of mineralization at the base than at the branch tips. The MgCO₃ concentration varied with genus and species and was between 9 and 11 mol %. The variation of the MgCO₃ concentration within different growth regions of the same species was small and generally did not exceed 0.8 mol %. From the branch to the stem, CaCO₃ and total mineral content was found to increase. The CaCO₃:MgCO₃ rations in different growth regions of all species indicated that the composition of the mesoskeleton with regard to the relative concentration of CaCO₃ and MgCO₃ is constant throughout the animal. Mineralogically, the mesoskeleton consists of high magnesian calcite as identified by X-ray diffraction. MgCO₃ concentrations determined by the peak shift method and by AAS were in fair agreement. The MgCO₃ data in gorgonian samples from the cold Atlantic Ocean and the warmer Indian Ocean show a linear relationship between water temperature and MgCO₃ concentration already demonstrated by Chave (1954). However, our data were consistently lower by 1 to 2% than expected.     

Elucidation of phosphorous sorption by calcareous soils using principal component analysis

This study was conducted to understand the mechanisms governing P-sorption and desorption by calcareous soils (up to 48% CaCO ₃). Batch experiments with KCl as background were carried out by adding varying amount of P up to 100 mgP.L^?1. The desorption percentage (%DES) results show that little P was released from the adsorbed phase. Principal component analysis was applied to evaluate the combined influence of soil components on P sorption. The complex P sorption process can be related to specific soil components by the following equation: P? sorption=?2.20 (CaCO ₃% )?0.04 (Fe? oxide)+0.04 (pHe)+11.02 (sand % )+3.35 (silt)?10.73 (clay)?1.24 (EC)?0.22 (OM)?0.81 (CEC)?1.93 (P? Olsen) (R²=0.9941, SSE=380). Sand% and clay% are the most significant variables for modelling P sorption data. The derived equation could be applied to predict P sorption in other soils that have similar compositions to those investigated herein. The degree of P saturation (DPS) threshold level for all soils was less than 3% except in the soil with the lowest iron oxide. All of the studied soils have exceeded the environmentally unacceptable P concentration except the soil with the lowest iron oxide content.