The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.     

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

Effective removal of coordinated copper from wastewater using a new dithiocarbamate-type supramolecular heavy metal precipitant

A new dithiocarbamate-type heavy metal precipitant, sodium 1,3,5-hexahydrotriazinedithiocarbamate (HTDC), was prepared and used to remove coordinated copper from wastewater. In the reported dithiocarbamate-type precipitants, HTDC possesses the highest percentage of the effective functional groups. It could effectively precipitate copper to less than 0.5 mg l⁻¹ from both synthetic and actual industrial wastewater containing CuEDTA in the range of pH 3–9. UV–vis spectral investigation and elemental analysis suggested that the precipitate was a kind of coordination supramolecular compound, [Cu₃(HTDC)₂]_n. The toxicity characteristic leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) indicated that the supramolecular precipitate was non-hazardous and stable in weak acid and alkaline conditions. Tests of an anion exchange resin D231 provided a clue to simultaneously remove excess HTDC and residual CuEDTA in practical process of wastewater treatment.     

污泥中重金属的去除及回收试验

论述了利用离子交换技术循环使用柠檬酸去除污泥中重金属,并置换回收重金属的适宜工艺条件.经柠檬酸处理后,污泥中90%以上的重金属被去除;柠檬酸处理液中的重金属用离子交换法回收,考察了树脂种类、流速、操作方式等因素对离子交换、再生效果的影响;在适宜工艺条件下,重金属的交换率均为100%,而洗脱率均接近90%;柠檬酸及离子交换树脂循环使用,重金属也得到回收,降低了处理成本.     

A comparative investigation on the biosorption of lead by filamentous fungal biomass

The removal of lead from aqueous solutions by adsorption on filamentous fungal biomass was studied. Batch biosorption experiments were performed to screen a series of selected fungal strains for effective lead removal at different metal and biomass concentrations. Biosorption of the Pb²⁺ ions was strongly affected by pH. The fungal biomass exhibited the highest lead adsorption capacity at pH 6. Isotherms for the biosorption of lead on fungal biomass were developed and the equilibrium data fitted well to the Langmuir isotherm model. At pH 6, the maximum lead biosorption capacity of Mucor rouxii estimated with the Langmuir model was 769 mg/g dry biomass, significantly higher than that of most microorganisms. Biomass of Mucor rouxii showed specific selectivity for Pb²⁺ over other metals ions such as Zn²⁺. Ni²⁺ and Cu²⁺. This fungal strain may be applied to develop potentially cost-effective biosorbent for removing lead from effluents. The technique of scanning electron microscopy coupled with X-ray dispersion analysis shows that Pb²⁺ has exchanged with K⁺ and Ca²⁺ on the cell wall of Mucor rouxii, thereby suggesting ion exchange as one of the dominant mechanisms of metal biosorption for this fungal strain.     

Kinetic studies of adsorption of thiocyanate onto ZnCl2 activated carbon from coir pith, an agricultural solid waste

The adsorption of thiocyanate onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of various parameters such as agitation time, thiocyanate concentration, adsorbent dose, pH and temperature has been studied. Adsorption followed second-order rate kinetics. Two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q₀) was found to be 16.2 mg g⁻¹ of the adsorbent. The per cent adsorption was maximum in the pH range 3.0–7.0. pH effect and desorption studies showed that ion exchange and chemisorption mechanism are involved in the adsorption process. Thermodynamic parameters such as ΔG⁰, ΔH⁰ and ΔS⁰ for the adsorption were evaluated. The negative values of ΔH⁰ confirm the exothermic nature of adsorption. Effects of foreign ions on the adsorption of thiocyanate have been investigated. Removal of thiocyanate from ground water was also tested.     

Removal of carbon disulfide via coupled reactions on a bi-functional catalyst: experimental and modeling results

A mathematical model describing the rate of carbon disulfide (CS₂) removal due to coupled reactions has been developed. Kinetic studies were carried out in a fixed bed reactor under atmospheric pressure and a range of temperatures (85–125 °C). The effects of flow rate, CS₂ inlet concentration, temperature and relative humidity were analyzed. A kinetic model based on axial dispersion, external and internal mass-transfer resistances, as well as effects of S deposition on the inner-face of the catalyst was in agreement with the CS₂ experimental breakthrough curves. The mathematical model can be used for process design and scale up of similar systems.     

As(V) adsorption on amorphous iron oxide: Triple layer modelling

The adsorption of As(V) by amorphous iron oxide was investigated at 25°C, 0.01 M NaNO₃ background electrolyte as a function of solution pH(4–10) at three initial As(V) concentrations and two Fe(III) concentrations. As(V) adsorption increased with decreasing pH. A modified Langmuir isotherm has been used for describing an equilibrium partition existing between solid and liquid phases. The triple-layer model was used for simulating As(V) adsorption on iron oxide surface. This model was able to describe As(V) adsorption over the pH range 4–10, all at the concentrations of As(V) and Fe(III) studied. =Fe(H₂AsO₄)⁰, = Fe(HAsO₄)⁻ and = Fe(AsO₄)²⁻ have been shown through simulation with inner-sphere complexation products to be more consistent with experimental adsorption observations than complexation with other surface species.     

Linear free energy relationships for dechlorination of aromatic chlorides by Pd/Fe

Reductive dechlorination rate constants for five chlorobenzenes in the presence of Pd/Fe as catalyst were determined experimentally. Linear free energy relationships (LFER) for the dechlorination rate constants of five chlorobenzenes and three chlorophenols were developed by partial least squares (PLS) regression based on quantum chemical parameters computed by PM3 Hamiltonian. The optimal LFER model obtained is

logk=−1.63+1.46×10⁻³ΔH_f−7.69×10⁻¹E_LUMO

where k stands for the dechlorination rate constants, ΔH_f is the standard heat of formation, and E_LUMO is the energy of the lowest unoccupied molecular orbital. The Q²_cum value of the model is 0.879, indicating good robustness and predictive power of the model.     

Removal of a cationic dye from aqueous solutions by adsorption onto bentonite clay

The ability of bentonite to remove malachite green from aqueous solutions has been studied for different adsorbate concentrations by varying the amount of adsorbent, temperature, pH and shaking time. Maximum adsorption of the dye, i.e. >90% has been achieved in aqueous solutions using 0.05 g of bentonite at a pH of 9. Thermodynamic parameters such as ΔH°, ΔS° and ΔG° were calculated from the slope and intercept of the linear plots of ln K_D against 1/T. Analysis of adsorption results obtained at 298, 308, 318 and 328 K showed that the adsorption pattern on bentonite seems to follow the Langmuir, Freundlih and D–R isotherms. The temperature increase reduces adsorption capacity by bentonite, due to the enhancement of the desorption step in the mechanism. The numerical values of sorption free energy (E_a) of 1.00–1.12 kJ mol⁻¹ indicated physical adsorption. The kinetic data indicated an intraparticle diffusion process with sorption being first order. The rate constant k was 0.526 min⁻¹. The concentration of malachite green oxalate was measured before and after adsorption by using UV–Vis spectrophotometer.     

Effect of La3+ on the activities of antioxidant enzymes in wheat seedlings under lead stress in solution culture

In order to improve the plant ability to resist lead stress, effect of 0.05 mg/l La(NO₃)₃ on the activities of catalase (CAT), superoxide dismutase (SOD), the level of malondialdehyde (MDA) in wheat seedlings under lead stress was studied. The effect of La³⁺ on plant growth, chlorophyll content in wheat seedlings after adding 0, 50, 100 mg/l Pb(NO₃)₃ to the nutrient solution for 12 days was observed. The plants were grown in nutrient solution in a strictly controlled climate growth room. Effects of La³⁺ (with La treatment) compared with check groups was evidently observed. The activities of SOD and CAT in root were enhanced 0.45–1.69 times and 33.20–77.77% respectively and MDA content was reduced 11.05–27.49% in root after treatments from the second day till the end of the experiment. The activities of SOD and CAT was found to be increased slightly (P<0.05) and MDA content decreased in shoot and root of wheat seedlings by La³⁺ under lead stress within five days after treatments compared with Pb1 and Pb2 groups. It was assumed that antioxidant enzymes was found to be increased by La(NO₃)₃, the antioxidant potential of the wheat seedlings to resist lead stress enhanced. It is suggested that La³⁺ could be used to resist lead stress at the beginning under stress while the stress was not so serious.     

Effects of pH on the toxicity of cadmium, copper, lead and zinc to Folsomia candida Willem, 1902 (Collembola) in a standard laboratory test system

EC₅₀s for cadmium, copper, lead and zinc were determined for juvenile production of Folsomia candida at pH6.0, 5.0 and 4.5 in a standard laboratory test system. In contrast to most previous studies where metal toxicity was increased at low pHs, in our experiments there was no clear relationship between soil acidity and EC_{50-reproduction} in this species. The EC_{50-reproduction} values (μg g⁻¹) for cadmium and zinc were similar at all three pHs (pH6.0: Cd 590, Zn 900; pH5.0: Cd 780, Zn 600; pH4.5: Cd 480, Zn 590). In contaminated field sites adjacent to primary zinc smelters, zinc is invariably present in soils at concentrations of at least 50 times that of cadmium Thus deleterious effects of mixtures of these metals on populations of Collembola in such sites can be attributed to zinc rather than cadmium.     

Can aquatic distribution of human pharmaceuticals be related to pharmacological data?

The recognition of pharmaceuticals as significant environmental contaminants has only been a recent phenomenon. Therefore there is a paucity of data relating to the fate and effects of pharmaceuticals once they enter an aquatic receiving system. The amount of work that needs to be done in terms of risk assessment for pharmaceuticals required by regulatory agencies is substantial. This paper has determined the environmental partitioning coefficient (K_d) of 13 diverse human pharmaceuticals in three model systems of differing combinations of solid phases and solutions. The K_d values were then compared with distribution values of the pharmaceuticals in the human body determined from pharmacological studies. This was done to assess the functional relationship between K_d and distribution values in the human body (V_D). K_d values ranged from 3 to 2450 L kg⁻¹. Regression coefficients ranged from r² = 0.62–0.72, indicating that V_D values are a useful indicator for the K_d values of the tested pharmaceuticals within the batch sorption systems. The relationship between K_d and V_D should therefore be further explored to determine whether this relationship can be applied to a broader range of pharmaceuticals in more diverse environmental systems. Exploiting available human pharmacological data in such a way would be of great benefit in prioritising human pharmaceuticals as environmental contaminants in the risk assessment process.     

Fenton''s type reaction and chemical pretreatment of PCBs

This study evaluates the effects of Fenton's reagent (FR) on the rate and extent of the oxidative degradation of individual mono, di-, tri- and tetrachlorobiphenyls in the commercial mixture DELOR 103, equivalent to AROCLOR 1248. The oxidation effect of FR strongly increased with increasing the molar ratio of Fe²⁺/H₂O₂. The most effective oxidation of DELOR 103 (10 μg.ml⁻¹) was achieved in a solution containing 1M H₂O₂ and 1 mM Fe²⁺. The FR elimination rate constants of PCB congeners decrease with increasing number of chlorine substituents in the biphenyl molecule and show a good correlation with the values of molecular weights of the PCB congeners and their 1-octanol/water partition coefficients.     

Compound-specific chlorine isotope analysis of polychlorinated biphenyls isolated from Aroclor and Clophen technical mixtures

The combined electrochemical oxidation-solar-light/immobilized TiO₂ film process was conducted to degrade an azo dye, Reactive Black 5 (RB5). The toxicity was also monitored by the Vibrio fischeri light inhibition test. The electrochemical oxidation rapidly decolorized RB5 (55, 110 μM) with a supporting electrolyte of 2 g l⁻¹ NaCl at current density 277 A m⁻² and pH 4. However, TOC mineralization and A₃₁₀ removal were low. Additionally, the treated solution showed high biotoxicity. RB5 at 110 μM significantly retarded the de-colorization efficiency by using the solar-light/immobilized TiO₂ film process. The combined electrochemical oxidation-solar-light/immobilized TiO₂ process effectively increased the removal of color, A₃₁₀, and TOC. The toxicity was also significantly reduced after 3 h of solar irradiation. The results indicated that the low-cost combined process is a potential technique for rapid treatment of RB5.     

锆负载型树脂用于含氟废水深度处理的研究

本文研制了一种以火力发电厂废树脂为载体的锆负载型氟离子吸附剂 ,并在评价了该树脂对氟离子的吸附性能之后探讨了该树脂用于火力发电厂含氟废水深度处理的可能性。研究结果表明 ,锆的最佳负载的最佳浓度为0 .5mol/L ,该负载树脂的最佳吸附pH为 3.0— 4 .0 ,用填充柱进行的动态实验结果表明 ,pH =3时的吸附容量显著高于 pH=4时的值。利用该树脂对火力发电厂模拟含氟废水进行了双柱串联吸附工艺处理 ,当柱流量为 35mL/min(SV10 )、第二柱穿透时 ,第一柱的吸附容量为 10 2 2 8mg/L湿树脂 ;用 0 .1mol/L的NaOH溶液进行再生 ,柱流量选择为 35mL/min(SV10 )时 ,脱附率在 95 %以上。     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 1-aliphatic hydrocarbons

The temporal variability and bioaccumulation dynamics of C_12–25 n-alkanes, isoprenoids and unresolved aliphatic hydrocarbons (UCM) were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the sewage impacted Buenos Aires coastal area. Fish muscles contain huge amounts of n-C_12–25 (165 ± 93, 70 ± 48 or 280 ± 134 μg g⁻¹, dry, fresh and lipid weight, respectively) and UCM (931 ± 560, 399 ± 288 and 1567 ± 802 μg g⁻¹) reflecting the chronic bioaccumulation of fossil fuels from sewage particulates. On a temporal basis, lipid normalized aliphatic concentrations peaked by the end of 2001–2002 during the rainiest period over the last four decades (1750 vs. 1083 ± 4.6 mm in 1999, 2004 and 2005), reflecting an enhanced exposition due to massive anthropogenic fluxes from Metropolitan Buenos Aires in wet years. The hydrocarbon composition in fish muscles is enriched in n-C_15–17 and isoprenoids relative to a fresh crude oil and settling particulates, with fresher signatures during the 2001–2002 maxima. Fish/settling material bioaccumulation factors (BAFs: 0.4–6.4 dry weight or 0.07–0.94 lipid-organic carbon) plotted against K_ow showed a parabolic pattern maximizing at n-C_14–18 and isoprenoids. The optimal bioaccumulation window corresponds to highly hydrophobic (log K_ow: 7.2–9.9), intermediate-size C_14–18 n-alkanes and C_15–20 isoprenoids (MW: 198–282; length: 17.9 to 25.4 Å) with melting points ranging from −19.8 to 28 °C. The uptake efficiency is inversely correlated to melting points and increased from 75% for n-C₂₅ to above 90% for n-C_14–15 and isoprenoids.     

Experimental Zn(II) retention in a sandy loam soil by very small columns

The use of column experiments, usually performed to better approximate field conditions, may provide information that is not available from batch experiments. In such experiments heavy metals are often adsorbed until saturation followed by desorption experiments. When the affinity of the metal to soil is high, the retention factor (R) could be greater than thousands and the duration of experiments can become impractically long. In order to use reasonable laboratory time, the flow rate should be increased or the column size decreased. The increase in flow rate produces undesirable kinetic and dispersion effects, so we used very small soil columns (pore volume = 0.31–0.70 ml) and relatively high flow rates (0.03–0.12 ml min⁻¹) in studies of Zn(II) adsorption and retention in soils. Conservative tracer flow column experiments under saturation conditions were carried out to determine flow parameters for different flow rates. Column pore volume (V_p), Peclet numbers (Pe) and longitudinal dispersion coefficients (D_L) were determined from breakthrough curves. The effect of type of electrolyte and ionic strength on the Zn(II) retention onto soil was determined. The influence of flow rate and bed height on the retention coefficient and on the mass transfer zone was also studied. The effect of different influent Zn(II) concentrations on the R values obtained was analyzed. Freundlich parameters from column experiments were compared with batch ones. The leaching efficiency of different electrolytes, salts of weak organic acids and EDTA was also studied.     

Copper complexation by dissolved organic matter and uncertainty assessment of their stability constants

The interaction of Cu with dissolved organic matter (DOM, extracted from an organic forest floor) was investigated and the resulting data was evaluated in terms of their uncertainty. The speciation of Cu over ‘free’ Cu (as analysed by diffusive gradients in thin films (DGT)), dissolved Cu–DOM complexes and precipitated Cu–DOM was determined as a function of pH (3.5, 4.0 and 4.5) and Cu/C ratio. The dissolved organically bound fraction was highest at pH 4.5, but this fraction decreased with increasing Cu/C ratio, which was observed for all pH levels. In the range of Cu/C=7×10⁻⁵–2.3×10⁻² (mol/mol) the precipitated fraction was very small. The speciation of both Al and Fe was not affected by increasing Cu concentrations. From a continuous distribution model using the Scatchard approach, we calculated the optimal fit and corresponding upper and lower 95% uncertainty bounds of the overall stability constants (K_o) with the shuffled complex evolution Metropolis (SCEM) algorithm. Although the optimal equation fitted the data very well, the uncertainty of the, according to literature, most reliable approach to establish stability constants, was still large. Accordingly, the usually reported intrinsic stability constants exhibited large uncertainty ranging from logK_i=6.0–7.1 (optimal 6.7) for pH 3.5, logK_i=6.5–7.1 (optimal 6.8) for pH 4.0, and logK_i=6.4–7.2 (optimal 6.8) for pH 4.5 and showed only little effect of pH.     

Sorption studies of heavy metal ions on a novel chelating resin and its application in the stripping of mercury (II)

A chelating resin containing a stable thiol group was synthesised, using polystyrene as the starting material. The resin is stable towards conc. HCl, 0.1M HNO(3) and 0.1M NaOH. The resin shows affinity towards Ag(+), Hg(2+), Bi(3+), Pb(2+), Cu(2+), Zn(2+) and Cd(2+). Extraction of these metal ions as a function of pH, kinetics of exchange and breakthrough capacities is evaluated. The selectivity of the resin for the metal ions is in the order Ag(+) > Hg2+ > Cu2+ > Pb2+ > Cd2+ > Zn2+. The equilibrium constants for exchange and kinetics of exchange are favourable for the recovery of mercury from lean sources. Application of the resin in the stripping of mercury from chlor-alkali plant affluent, and in the enrichment of mercury from seawater, have been investigated. Mercury sorbed resin can be regenerated using 5% thiourea in 0.1M HCl.