Modelling the absorption and desorption of cadmium on paper pulp using kinetic approaches

The presence of toxic metals on paper pulp and the migration of these metals to food from the food package is receiving significant attention. The final exposure levels for consumers depend on two main processes. First the potential of metals to bind paper pulp during manufacture. Second, the metal potential to migrate from paper to food during storage and use. Binding and unbinding processes are modelled for cadmium kinetics through kinetic approaches. The cadmium concentration in paper pulp is estimated from the cadmium concentration in the water-pulp liquor during manufacture, the temperature, and contact time. Two food simulants have been employed for desorption studies, water and acetic solution (3%, w/w). As expected, under acidic conditions desorption is total and rapid (close to 100% desorption reached in a few minutes). However, the desorption of cadmium into the neutral food simulant depends on the initial cadmium concentration in the paper pulp, temperature and contact time. Surface response curves for each combination are presented. Temperature did not affect cadmium binding, but played a significant role for the desorption processes into the neutral food simulant. The proposed equations offer a good fitting of the experimental values, with p < 0.001 and residuals within a factor of 3 for over 99% of the measured data. These models allow estimations of the expected exposure levels in consumers, on the basis of manufacture and use conditions. Linking the expected exposure with toxicity thresholds, such as the admissible daily intake (ADI), would allow a scientific assessment of the maximum acceptable cadmium levels in water-pulp liquors during manufacture and in the final paper pulp on the basic of the use patterns of each food packaging material.     

Speciation and mobility of cadmium in straw and wood combustion fly ash

Two fly ashes from biomass combustion have been analysed regarding cadmium speciation and mobility. A fly ash from straw combustion contained 10 mg Cd/kg dry matter, and around 50% of the cadmium was leachable in water. The possible main speciation of cadmium in this fly ash was CdCl2. When adding this fly ash to agricultural soil a threat for groundwater contamination and plant uptake is existing. A fly ash from wood chip combustion had 28.6 mg Cd/kg dry matter. In this fly ash, the cadmium was bound more heavily, with only small amounts of cadmium leached in mild extractants. A possible speciation of cadmium in this fly ash was as oxide or as CdSiO3. Long-term effects and accumulation of cadmium could be a problem when adding this fly ash to agricultural or forest soils.     

污泥果肥利用中重金属迁移特征研究

为了厦门城市污泥的安全利用,将石渭头污水处理厂污泥经过好氧堆肥后施用于柚子树,对重金属元素在土壤、树叶及果肉中的迁移特征进行了研究。结果表明：Cd在土壤中的富集能力强;重金属元素从土壤向树叶迁移累积能力比向果肉的大得多,污泥肥料不能用于叶类食用植物的施用;Cr向树叶、Ni向果肉的迁移累积能力强;泥肥的施用加重了土壤中Cd的污染,提高了Cr向树叶、Ni向果肉的迁移能力;污泥果肥利用需降低Ni的浓度,对污泥中含量较高的Cu、Zn、Ni、Cr和Cd需进行跟踪检测。     

The influence of humic acids on the phytoextraction of cadmium from soil

Cadmium poses a major environmental and human health threat because of its constant release through anthropogenic activities. A need, therefore, exists for cost-effective remediation procedures. Phytoremediation, the use of plants to extract contaminants from soils and groundwater, has revealed great potential. However, it is limited by the fact that plants need time, nutrient supply and, moreover, have a limited metal uptake capacity. Synthetic chelators have shown positive effects in enhancing heavy metal extraction through phytoremediation, but they have also revealed a vast number of negative side-effects. The objective of this research was to investigate the use of humic acids as an alternative to synthetic chelators. Humic acids were applied to a cadmium-contaminated soil at various dosages, and the uptake of cadmium into Nicotiana tabacum SR-1 was determined in relation to the amounts of total and bioavailable cadmium in the soil. It was found that the theoretical bioavailability of cadmium, as determined by diethylenetriaminepentaacetic acid (DTPA) extraction, did not change, but its plant uptake was enhanced significantly, in some cases up to 65%. Humic acids added at a rate of 2 g kg(-1) soil increased the cadmium concentration in the shoots from 30.9 to 39.9 mg kg(-1). A possible reason for this enhancement is the decrease in pH, resulting in higher cadmium availability. Another possibility taken into account is that plants may take up cadmium complexes with humic acid fragments, which result from microbiological degradation or, self-dissociation.     

The relationship between lead and cadmium levels and functional dependence among elderly participants

The adverse impacts of lead and cadmium exposure on health outcomes have been reported in the past. Few studies have been conducted on the relationship between lead and cadmium exposures and disability. We evaluated whether lead and cadmium exposures were associated with functional dependence including the total number of disabilities, activities of daily living (ADL), instrumental activities of daily living (IADL), leisure and social activities (LSA), lower extremity mobility (LEM), and general physical activities (GPA) in an elderly population. A total of 5513 eligible subjects were enrolled in the study from the National Health and Nutrition Examination Survey 2001–2006. Serum lead and cadmium exposure assessments were performed using atomic absorption spectrometry. Functional dependence was assessed by 19 structured questions. The relationships between lead and cadmium exposures and functional dependence were investigated using by multivariable linear regression models. Q2, Q3, and Q4 of lead exposure were significantly associated with the total number of disabilities, with β coefficients of ??0.62 (95% CI ??0.99, ??0.24), ??0.64 (95% CI ??1.02, ??0.26), and ??0.81 (95% CI ??1.19, ??0.42), respectively. This relationship remained significant in males. Furthermore, we analyzed the relationships between lead and cadmium exposure quartiles and various functional dependence metrics, and we determined that lead content was significantly associated with decreased ADL, LEM, and GPA (p?<?0.05) and cadmium content was inversely associated with ADL (p?<?0.05). Our study demonstrated a strong relationship between exposure to lead and cadmium and functional dependence in an elderly population.

     

液桥凝聚用于办公废纸脱墨的研究

研究了混合办公废纸脱墨的选择性凝聚技术,在废纸浆中添加分散在水中并不与水相溶的长链烷作凝聚剂,这些凝聚剂选择性地将印刷墨粉通过液桥连结在一起,且形成大颗粒的球形聚团,再分选脱除.研究表明只需要加入占纸重量4%的廉价长链烷,即可获得95%以上的脱墨率.因此在混合办公废纸脱墨时加入凝聚剂进行液桥凝聚,可降低脱墨浆中的尘埃度并增加产品的白度.     

Changes in concentration of lead and cadmium in water from three rivers in Derbyshire

River water from three sites in different streams in Derbyshire was sampled during different periods within 1 year to evaluate fluctuations in cadmium and lead concentration. The results indicate that most of the cadmium was in solution, while most of the lead was associated with particles at all sites. Period of sampling appeared to have a greater effect on the concentration of cadmium and lead than flow rate: metal levels were higher in spring than in autumn. Nevertheless, the total lead concentration increased with flow rate, presumably because more particles were then brought into suspension; however, the lead concentration in the filtrate was reduced at higher flow rates, presumably due to dilution in the greater water volume. Dissolved cadmium concentration increased with rising flow rate at relatively low flow rates and was diluted at high flow rates. The data suggest that particles with which most of the lead is associated remain in suspension for a considerable time even when flow rate decreases.     

Mobility of arsenic, cadmium and zinc in a multi-element contaminated soil profile assessed by in-situ soil pore water sampling, column leaching and sequential extraction

Three methods for predicting element mobility in soils have been applied to an iron-rich soil, contaminated with arsenic, cadmium and zinc. Soils were collected from 0 to 30 cm, 30 to 70 cm and 70 to 100 cm depths in the field and soil pore water was collected at different depths from an adjacent 100 cm deep trench. Sequential extraction and a column leaching test in the laboratory were compared to element concentrations in pore water sampled directly from the field. Arsenic showed low extractability, low leachability and occurred at low concentrations in pore water samples. Cadmium and zinc were more labile and present in higher concentrations in pore water, increasing with soil depth. Pore water sampling gave the best indication of short term element mobility when field conditions were taken into account, but further extraction and leaching procedures produced a fuller picture of element dynamics, revealing highly labile Cd deep in the soil profile.     

Copper and cadmium removal from synthetic industrial wastewater using chitosan and nylon 6

Purpose

Chitosan with nylon 6 membranes was evaluated as adsorbents to remove copper and cadmium ions from synthetic industrial wastewater.

Methods

Chitosan and nylon 6 with glutaraldehyde blend ratio with (1:1+Glu, 1:2+Glu, and 2:1+Glu) have been prepared and these were used as membranes to remove copper and cadmium ions from synthetic industrial wastewater. Characterization of the synthesized membrane has been done with FTIR, XRD, TGA/DTA, DSC, and SEM. Chemical parameters for quantities of adsorption of heavy metal contamination have been done and the kinetics of adsorption has also been carried out.

Results

The optimal pH for the removal of Cd(II) and Cu(II) using chitosan with nylon 6. Maximum removal of the metals was observed at pH 5 for both the metals. The effect of adsorbent dose also has a pronounced effect on the percentage of removal of the metals. Maximum removal of both the metals was observed at 5 g/100 ml of the adsorbent.

Conclusion

Copper and cadmium recovery is parallel at all time. The percentage of removal of copper increased with increase in the pH from 3 to 5. In the case of cadmium containing wastewater, the maximum removal of metal occurred at pH 5. The uptake amount of Cu²⁺ ions on chitosan increased rapidly with increasing contact time from 0 to 360 min and then reaches equilibrium after 360 min; the equilibrium constant for copper and cadmium ions is more or less the same for the adsorption reaction.     

Cadmium background content in meat,liver and kidney from cattle and its consequences to cadmium tolerance levels (x)

The natural background of cadmium content in meat, liver and kidney from 287 cattle from a non polluted area in the subalpine region of Bavaria has been analyzed during the period from 1972 to 1975. The cadmium content in meat was always below the detection limit of 0.005, in liver between < 0.005 to 1.65 (median 0.050) and in kidney 0.008 to 1.95 (median 0.229) ppm Cadmium in fresh weight. The cadmium contents are discussed and compared with preliminary suggestions for cadmium tolerance levels and their consequence for food inspection.     

Cadmium in the Amazonian Guajará Estuary: distribution and remobilization

Extremely high total cadmium concentrations (average about 500 mg/kg) together with very small (average of 1.1 microg/l) dissolved available cadmium have been found in the more acidic deeper layers of the bottom sediments of the Brazilian Amazonian Guajará Estuary. The paper shows that climatic changes and the periodic input of the Atlantic waters into the Estuary appear to have no direct influence on annual average total cadmium concentration, but they affect accumulation, distribution and remobilization of cadmium in different ways during the rainy season (February/March) and the dry season (November/December). Even if only a very small part of the total Cd is available, the concentrations of dissolved Cd in the Estuary are still high enough to cause environmental concern, if compared with concentrations in natural freshwater ecosystems.     

Single and double metallothionein knockout in the nematode C. elegans reveals cadmium dependent and independent toxic effects on life history traits

The genome of the nematode Caenorhabditis elegans contains two metallothionein genes, both involved in metal homeostasis and/or detoxification. Single metallothionein knockout mutants have been created and now, for the first time, a double mutant has been isolated. Life history studies in the presence or absence of cadmium showed that all metallothionein mutants are viable. Although cadmium did not influence longevity, a dose dependent reduction in total brood size and volumetric growth was observed in wild type animals, which was magnified in single knockouts and further exacerbated in the double knockout. However, the metallothionein deletion caused two effects that are independent of cadmium exposure, namely all knockout strains displayed a reduced total brood size and the deletion of both metallothionein loci caused a significant reduction in volumetric growth. In summary, metallothionein is undoubtedly an important player in cadmium detoxification, but evidently also an important factor in cadmium independent pathways.     

Long-term effects of soil heterogeneity on cadmium behaviour in soil

A deterministic model for long-term behaviour of contaminants in the rootzone is developed that includes sorption, leaching, and plant uptake. The model is applied to cadmium accumulation in a sandy soil and uptake of cadmium by barley. Sensitivity analysis showed that the sensitivity of the leaching rate to changes in soil chemical and soil physical parameters decreases as a function of time, and becomes zero when steady state is reached. In contrast, accumulation of cadmium in soil and the plant uptake rate of barley are increasingly sensitive to soil chemical and soil physical parameters as time preceeds. To analyse cadmium behaviour in a field that is heterogeneous with respect to soil physical properties, the interstitial flow velocity was assumed to be a random, lognormally distributed variate. Using Monte Carlo simulation, the average plant uptake rate appeared to be much higher in the stochastic analysis than in the deterministic approach. Steady state is reached after a very long period of time. For a lognormally distributed proton activity, causing heterogeneity with respect to the sorption capacity of the soil, the model predicted similar deviations from the deterministic approach. It is concluded that reference values for groundwater and crop quality are exceeded earlier in a heterogeneous field than in a homogenous soil profile. Moreover, when average values suggest an acceptable situation, variability of the leaching rate and the plant uptake rate can still cause exceedance of reference values in part of the field. Therefore, it is reasoned that environmental quality standards should take soil heterogeneity into account.     

Simultaneous removal of phenanthrene and cadmium from contaminated soils by saponin, a plant-derived biosurfactant

Batch experiments were conducted to evaluate the performance of saponin, a plant-derived biosurfactant, for simultaneously removing phenanthrene and cadmium from the combined contaminated soils. Results showed that phenanthrene was desorbed from the contaminated soils by saponin with the partition of phenanthrene into surfactant micelle, meanwhile cadmium was effectively removed from the contaminated soils by the complexation of cadmium with the external carboxyl groups of saponin micelle. The efficiencies of saponin for the removal of phenanthrene and cadmium from the contaminated soils were greater than that of Triton X100 and citric acid, respectively. At concentration of 3750 mg/L, saponin has a removal rate of 87.7% and 76.2% of cadmium and phenanthrene, respectively, from the combined contaminated soil. The removals of cadmium and phenanthrene from the soils were not obviously constrained each other. Thus, saponin has the potential for the removal of heavy metal and PAHs from the combined contaminated soils.     

Influence of clay on the adsorption of heavy metals like copper and cadmium on chitosan

The influence of clay on the adsorption of heavy metals like copper and cadmium on chitosan from simulated industrial wastewater is evaluated. Chitosan–clay blend with ratio of (1:1), (1:2), and (2:1) have been prepared, and these were used as membranes to remove copper and cadmium ions from synthetic industrial wastewater. The chemical parameters for quantities of adsorption of heavy metal contamination have been done, and the kinetics of adsorption has also been carried out. Clay provides enough absorbable sites to overcome mass transfer limitations. The number of absorbable sites for cadmium is more compared to copper, and thus the rate of recovery of cadmium is faster than copper, and the percentage removal of cadmium is more than copper at all times on clay over nylon 6. This difference indicates the influence of clay in the adsorption of heavy metals in comparison to synthetic polymer nylon 6. Rate constant for first-order kinetics of adsorption, k ₁, for copper and cadmium is less than that of clay, which clearly indicates that clay, which is a natural polymer, is more kinetically favored compared to synthetic polymer. The difference in the intraparticle diffusion in both the natural and synthetic polymer is not much, and it suggests that the particle diffusion mechanism is the same in both cases. Copper and cadmium recovery is parallel at all times. The percentage of removal of copper increased with an increase in pH from 3 to 5. In the case of cadmium containing wastewater, the maximum removal of metal occurred at pH 5. The uptake amount of Cu²⁺ ions on chitosan increased rapidly with increasing the contact time from 0 to 360 min and then reaches equilibrium after 360 min, and the equilibrium constant for copper and cadmium ions are more or less the same for the adsorption reaction. There are more adsorption sites for cadmium in the presence of clay and mass transfer limitation is avoided without resorting to rotation, which is the highlight of the present work. And more so, this is pronounced in the case of natural polymer compared to synthetic polymer.     

Lipophilic extractives in process waters during manufacturing of totally chlorine free kraft pulp from eucalypt wood

The chemical composition of lipophilic extractives from process waters throughout a totally chlorine free (TCF) bleaching sequence after kraft pulping of eucalypt wood has been studied. These compounds are among the most problematic wood constituents for both TCF and zero liquid effluent (ZLE) processes, since they tend to accumulate in circuits resulting in the formation of the so-called pitch deposits causing serious problems in the pulp and paper industry. Pitch deposits collected at different parts of the pulp mill were also characterized and their composition compared with that of lipophilic compounds in process waters and Eucalyptus globulus wood. The identification of these compounds from process waters, wood and pitch deposits was performed by gas chromatography and gas chromatography-mass spectrometry using short- and medium-length high temperature capillary columns. Sterols, sterol esters, steroid ketones and steroid hydrocarbons were the main compounds identified. These chemical species arise from eucalypt wood extractives that survive the pulping and are released from pulp into the process waters during the bleaching process. Finally, they can deposit in pulp and on different parts of the mill or remain suspended in process waters being discharged in effluents.     

The current status of osteoporosis after 15 years of reduced cadmium exposure among residents living in cadmium-contaminated areas in northwestern Thailand

The purposes of this study were to determine the prevalence of osteoporosis after 15 years of reduced cadmium exposure and to determine the association between urinary cadmium (U-Cd) and osteoporosis. The study was conducted with 937 participants (109 males, 828 females) living in a cadmium-contaminated area in northwestern Thailand. All participants were required to respond to a questionnaire. Bone mineral density (BMD) was investigated by measurements taken at the calcaneus by dual-energy X-ray absorptiometry. U-Cd, which reflects the amount of cadmium contained in the body, was measured by atomic absorption spectrophotometry (AAS). The geometric mean of U-Cd was significantly higher in males than in females (p < 0.001). The mean level of BMD for females was found to be statistically significantly lower than that for males (p < 0.001). Increasing U-Cd levels were correlated with decreasing levels of BMD. The association between U-Cd and osteoporosis appeared to exist only at concentrations of U-Cd ≥ 10 μg/g creatinine (OR = 2.7, 95% CI = 1.2–5.9). It can be concluded that despite discontinued or reduced cadmium exposure for more than 10 years, the effect of cadmium toxicity on bone, which is stronger in women, continues, as cadmium, once absorbed, will accumulate in the human body for a long time due to its extremely long half-life.

     

Antimony distribution and environmental mobility at an historic antimony smelter site, New Zealand

A historic antimony smelter site at Endeavour Inlet, New Zealand has smelter residues with up to 17 wt.% antimony. Residues include coarse tailings (cm scale particles, poorly sorted), sand tailings (well sorted) and smelter slag (blocks up to 30 cm across). All of this material has oxidised to some degree over the ca. 100 years since the site was abandoned. Oxidation has resulted in acidification of the residues down to pH 2-5. Smelter slag contains pyrrhotite (FeS) and metallic antimony, and oxidation is restricted to surfaces only. The coarse tailings are the most oxidised, and few sulfide grains persist. Unoxidised sand tailings contain 10-20 vol.% stibnite (Sb2S3) containing up to 5% As, with subordinate arsenopyrite (FeAsS), and minor pyrite (FeS2). The sand tailings are variably oxidised on a scale of 2-10 cm, but original depositional layering is preserved during oxidation and formation of senarmontite (Sb2O3). Oxidation of sand tailings has resulted in localised mobility of both Sb and As on the cm scale, resulting in redistribution of these metalloids with iron oxyhydroxide around sand grain boundaries. Experiments demonstrate that Sb mobility decreases with time on a scale of days. Attenuation of both As and Sb occurs due to adsorption on to iron oxyhydroxides which are formed during oxidation of the smelter residues. There is no detectable loss of Sb or As from the smelter site into the adjacent river, <50 m away, which has elevated Sb (ca. 20 microg/l) and As (ca. 7 microg/l) from mineralised rocks upstream. Despite the high concentrations of Sb and As in the smelter residues, these metalloids are not being released into the environment.     

In situ cadmium reclamation by freshwater bivalve Lamellidens marginalis from an industrial pollutant-fed river canal

The biofilter potential of the freshwater bivalve, Lamellidens marginalis was examined in cage experiments conducted in a river canal (Ichhapore, 24-Parganas, West Bengal, India) receiving industrial effluents from steel and metal factories as well as from an ordinance factory. Cadmium is one of the major contaminants in this river canal. Lamellidens collected from pollution free natural ponds, were sorted into three size groups (large: 59+/-3.2 g, 10+/-2.3 cm; medium: 30+/-2 g, 6+/-1.7 cm and small: 13+/-1.5 g, 4+/-1.2 cm) were held in cages at three different sites along a cadmium concentration gradient. Concentrations of cadmium were measured from water, sediment and different tissues of Lamellidens at weekly intervals using atomic absorption spectrophotometric methods. Cadmium uptake by Lamellidens in all media were highly concentration dependent in both summer and winter months. For all three size groups, cadmium uptake was maximum in the gills at the beginning of experiment, and liver at the later phase. Cadmium uptake was maximum in the small bivalves and minimum in the large bivalves groups. Cadmium uptake was 11-67% higher during summer than during the monsoon season for all tissues and size groups. Estimation of concentration factor revealed that tissues were saturated with cadmium during the 13-14th week after Lamellidens introduction during summer, but remained unsaturated during the monsoon season. It is concluded that Lamellidens might be considered as an efficient biofilter for reclamation of aquatic environment having sub-lethal concentrations of cadmium.     

Evaluation of Kraft Process Pollution Abatement Strategies by Time Series Analysis of Makeup Records

A historical record of monthly chemical makeups for a North American pulp mill has been analyzed by time series methods. The analysis yields estimates for the reduction in sulfur makeup resulting from each of three separate pollution abatement moves: black liquor oxidation, blow heat recovery, and cooking liquor sulfidity reduction. Further analysis yields estimates of sulfurous emissions and of the substantially lower emissions which could have been achieved if sulfidity management had been incorporated in the program.