Comparative studies on the biokinetics of Cd, Cr, and Zn in the green mussel Perna viridis and the Manila clam Ruditapes philippinarum

A kinetic approach was employed to determine the rates of metal uptake (Cd, Cr and Zn) from the dissolved phase and the rate constants of metal depuration in the mussel Perna viridis and the clam Ruditapes philippinarum. The effects of ambient metal concentration, salinity, and body size on the metal influx rate were examined. A linear positive relationship was observed between the metal influx rate and the metal concentration in ambient seawater. There was some evidence that Zn uptake was regulated by the bivalves in response to an increase in ambient Zn concentration. The uptake rate constant was highest for Zn and lowest for Cr in both bivalves, and was higher in mussels than in clams. The metal influx rate decreased by 1.6-1.8 times for the three metals when the salinity was increased from 15 ppt to 30 ppt. However, the effect of salinity on Zn influx in mussels was not statistically significant. A negative relationship of Cd and Zn influx rates with tissue dry weight was also found in both bivalves. Cr uptake in mussels was not significantly correlated with body size, but its uptake in clams was significantly correlated with body size. Metal concentration in ambient seawater appeared to be the most determining factor on metal uptake from the dissolved phase in both bivalves. The efflux rate constants of the three metals were within the range of 0.01-0.03 d-1, and were comparable between the mussels and the clams. Using a simple bioenergetic-based kinetic model, it was shown that both dissolved uptake and food ingestion can contribute to metal accumulation in the bivalves. However, Zn accumulation in the clam R. philippinarum was dominated by uptake from food ingestion. Metal partitioning in ingested food was found to be critical in affecting the relative importance of metal uptake from the dissolved phase and food source, primarily because of the large variability of this parameter in natural environments.     

Modelling of the acid-base properties of natural and synthetic adsorbent materials used for heavy metal removal from aqueous solutions

In this paper a comparison about kinetic behaviour, acid-base properties and copper removal capacities was carried out between two different adsorbent materials used for heavy metal removal from aqueous solutions: an aminodiacetic chelating resin as commercial product (Lewatit TP207) and a lyophilised bacterial biomass of Sphaerotilus natans. The acid-base properties of a S. natans cell suspension were well described by simplified mechanistic models without electrostatic corrections considering two kinds of weakly acidic active sites. In particular the introduction of two-peak distribution function for the proton affinity constants allows a better representation of the experimental data reproducing the site heterogeneity. A priori knowledge about resin functional groups (aminodiacetic groups) is the base for preliminary simulations of titration curve assuming a Donnan gel structure for the resin phase considered as a concentrated aqueous solution of aminodiacetic acid (ADA). Departures from experimental and simulated data can be interpreted by considering the heterogeneity of the functional groups and the effect of ionic concentration in the resin phase. Two-site continuous model describes adequately the experimental data. Moreover the values of apparent protonation constants (as adjustable parameters found by non-linear regression) are very near to the apparent constants evaluated by a Donnan model assuming the intrinsic constants in resin phase equal to the equilibrium constants in aqueous solution of ADA and considering the amphoteric nature of active sites for the evaluation of counter-ion concentration in the resin phase. Copper removal outlined the strong affinity of the active groups of the resin for this ion in solution compared to the S. natans biomass according to the complexation constants between aminodiacetic and mono-carboxylic groups and copper ions.     

硫化镍异相结晶法处理含镍废水

针对含络合剂的重金属废水,以含镍废水为例,探索了以气体硫化氢为结晶药剂的硫化镍异相结晶技术。废水以薄层液膜方式铺展于结晶载体表面,硫化氢气体穿过气液界面进入液相,硫离子与金属离子在载体表面异相结晶析出,重金属得以去除。以含酒石酸的模拟化学镀镍废水为对象,静态实验与动态实验均表明该技术具有可行性,硫化镍沉淀在结晶载体表面异相结晶析出,且附着稳定;络合剂对反应影响小;进水流速为4 mL/min,硫化钠流速为0.65 g/min,氮气流速为0.16 L/min时,出水镍浓度为49～53 mg/L,单位面积滤布表面结晶平均去除镍量为0.98 g/(m2.h)。     

Tissue distribution of inorganic mercury, methylmercury and cadmium in the Asiatic clam (Corbicula fluminea) in relation to the contamination levels of the water column and sediment

The comparative experimental study of inorganic mercury (HgII), methylmercury (MeHg) and cadmium (Cd) bioaccumulation in the Asiatic clam Corbicula fluminea was based on a 14 days' exposure to the water column or sediment compartments, as initial contamination sources. For each contaminant and exposure source, a five-point concentration range was set up in order to quantify the relationships between the contamination pressure and bioaccumulation capacity, at the whole soft body level and in five organs: gills, mantle, visceral mass, kidney and foot. Hg and Cd bioaccumulation at the whole organism level was proportional to the metal concentrations in the water column or sediment. For similar exposure conditions, the average ratios between the metal concentrations in the bivalves - [MeHg]/[HgII] and [MeHg]/[Cd] - were close to 10 and 5 for the sediment source and 8 and 15 for the water column source. Metal distribution in the five organs revealed strong specificities, according to the different contamination modalities studied: kidney and gills were clearly associated with Cd exposure, mantle and foot with MeHg exposure and the visceral mass with inorganic Hg exposure.     

Chromium (III) removal by supported liquid membranes: a comparison among D2HEPA, DNNSA, and a novel extractant as carriers.

A facilitated transport study in supported liquid membranes (SLM) using the extraction reagents di-2-ethylexilfosphoric acid (D2HEPA), dinonylnaftalene sulfuric acid (DNNSA), and a novel complexing agent, trimethyl cis,cis-1,3,5-tripropyl-1,3,5 cyclohexenetricarboxilic acid (TTCHTCA) as carriers has been carried out. Organic solvents with different dielectric constants as diluents have been used to obtain the highest extraction and transport values. The results obtained have shown that, by using different organic phases (carrier and/or diluent), SLMs with different ion flux and transport ability can be obtained. The carrier concentration in the membrane and the chromium (III) [Cr(III)] ions concentration in aqueous phase have been varied to see the effect on transport of Cr(III) ions across the membrane. For the carriers D2HEPA and TTCHTCA, the transport of Cr(IlI), both in batch and in recirculation operation mode, has been studied. Very good results in terms of flux and transport have been obtained using TTCHTCA.     

Estimation of atmospheric trace metal emissions in Vilnius City, Lithuania, using vertical concentration gradient and road tunnel measurement data

A new approach for the estimation of trace metal emissions in Vilnius city was implemented, using vertical concentration profiles in the urban boundary layer and road tunnel measurement data. Heavy metal concentrations were examined in fine and coarse particle fractions using a virtual impactor (cut-off size diameter 2.5 μm). Negative vertical concentration gradients were obtained for all metals (Ba, Pb, V, Sb, Zn) and both fractions. It was estimated that the vertical concentration gradient was formed due to emissions from an area of about 12 km². Road tunnel measurements indicated that trace metal concentrations on fine particles were lower than those on coarse particles, which suggested that re-emitted road dust was highly enriched in trace metal due to historic emissions within the tunnel. Emission rates of different pollutants in the road tunnel were calculated using pollutant concentration differences at the tunnel entrance and exit and traffic flow data. Heavy metal emission rates from the area of Vilnius city were estimated using the vertical gradient of heavy metal concentrations and the coefficient of turbulent mixing, as derived from meteorological measurement data. The emission values calculated by the two different methods coincided reasonably well, which indicated that the main source of airborne trace metals in Vilnius city is traffic. The potential of the vertical concentration gradient method for the direct estimation of urban heavy metal emissions was demonstrated.     

Humic acid enhanced remediation of an emplaced diesel source in groundwater. 2. Numerical model development and application

A pilot scale experiment for humic acid-enhanced remediation of diesel fuel, described in Part 1 of this series, is numerically simulated in three dimensions. Groundwater flow, enhanced solubilization of the diesel source, and reactive transport of the dissolved contaminants and humic acid carrier are solved with a finite element Galerkin approach. The model (BIONAPL) is calibrated by comparing observed and simulated concentrations of seven diesel fuel components (BTEX and methyl-, dimethyl- and trimethylnaphthalene) over a 1500-day monitoring period. Data from supporting bench scale tests were used to estimate contaminant-carrier binding coefficients and to simulate two-site sorption of the carrier to the aquifer sand. The model accurately reproduced the humic acid-induced 10-fold increase in apparent solubility of trimethylnaphthalene. Solubility increases on the order of 2-5 were simulated for methylnaphthalene and dimethylnaphthalene, respectively. Under the experimental and simulated conditions, the residual 500-ml diesel source was almost completely dissolved and degraded within 5 years. Without humic acid flushing, the simulations show complete source dissolution would take about six times longer.     

不同填料载体生物膜对微囊藻毒素的去除效果

利用自行设计的生物膜培养装置,通过对4种不同填料载体进行连续曝气循环培养生物膜,对湖水中的溶解态微囊藻毒素(MCs)的去除作用进行了研究。结果表明,填料载体上生物膜从形成到稳定大约需要3周;生物膜形成后对MCs的去除效率由高到低的顺序是:颗粒活性炭柱>多密孔球型滤料柱>塑料悬浮填料柱>陶瓷滤球柱。在实验水质条件下,当水力停留时间(HRT)=5 h,进水MCs浓度为21.5～47.25μg/L时,颗粒活性炭、多密孔球型滤料柱对MCs的去除率最高可达100%,塑料悬浮填料柱对MC-LR和MC-RR的去除率分别为70%和88%。当HRT=2.5 h时,塑料悬浮填料柱对MC-RR的去除率为MC-LR的2倍。生物膜对MCs的降解效果随温度(5～20℃)和溶解氧的升高而增加。塑料悬浮填料作为合适的生物膜挂膜填料载体对水源水的生物预处理具有良好的应用前景。     

Effect of bone meal (calcium phosphate) amendments on metal release from contaminated soils--a leaching column study

Metal-contaminated soil may be remediated in situ by the formation of highly insoluble metal phosphates if an appropriate phosphorus (P) source can be found. Leaching column experiments have been carried out to assess the suitability of bone meal as such a source. Bone meal additions reduced metal release from a contaminated soil, increased soil and leachate pH and decreased soil leachate toxicity. Minimal P leaching occurred from the soil. The data are consistent with a proton consuming bone meal (calcium phosphate) dissolution reaction followed by the formation of metal phosphates. Although, no metal phosphates were observed to form using X-ray diffraction of scanning electron microscopy this could be due to their low concentration. Relatively low (1:50 bone meal:soil) concentrations of fine (90-500 microns) bone meal would appear to be an effective treatment for metal-contaminated soils.     

Cadmium and methylmercury bioaccumulation by nymphs of the burrowing mayflyHexagenia rigida from the water column and sediment

Based on a three compartment microcosm-water column, natural sediment,Hexagenia rigida nymphs-an experimental study was set up to compare cadmium (Cd) and methylmercury (MeHg) bioaccumulation by a burrowing mayfly species, after exposure via the water column or the sediment as initial contamination sources. Results from a wide concentration range for each exposure condition revealed very marked differences between the two metals: MeHg was readily accumulated from the two contamination sources, leading to important metal concentrations in the nymphs after the 2 weeks’ exposure; Cd bioaccumulation, on the other hand, was negligible when the metal was added to the water compartment, even though significant transfers were observed from the sediment source. The average Cd concentrations in the nymphs were proportional to the sediment contamination levels. Turbidity measurements in the water column, reflecting the bioturbation activity of the nymphs, revealed that the effect of Cd was significant, but only when the metal was initially added to the sediment. The results are discussed according to the uptake routes and the structural and functional properties of the biological barriers involved (gills and gut).     

介质阻挡放电氧化降解木质素磺酸钠的动力学研究

为了有效地处理难生物降解的造纸废水,采用气相介质阻挡放电产生氧化性物质,对木质素磺酸钠进行了氧化降解研究。在不同操作条件下,对其降解动力学及矿化程度进行了研究。结果表明,介质阻挡放电能有效地降解木质素磺酸钠,其氧化降解反应遵循准一级动力学反应。当峰值电压为20 kV,被水蒸气饱和的空气为气源,流量为7 L/min时,氧化处理60 min后,木质素磺酸钠降解率达到70％。其速率常数K随峰值电压、气源、气体流量和木质素磺酸钠的初始浓度的变化而不同。气体流量越大,木质素磺酸钠的初始浓度越低,速率常数K越大,降解效果越好。随着处理时间的增加,氧化性物质能将部分木质素磺酸钠矿化使溶液TOC降低,当被水蒸气饱和的空气作为气源时,氧化处理120min,21.38%的TOC被去除。     

110离子交换树脂担载催化齐净化低浓度PH3

以110丙烯酸系阳离子交换树脂作为载体,Pd（Ⅱ）-Cu（Ⅱ）为主催化剂,制成担载型过渡金属催化剂。以N2为载气,对反应温度、氧含量、催化剂用量3个因素进行催化氧化净化低浓度PH3研究。实验结果表明,在氧含量为3．7％,温度为72℃时,催化剂的催化活性较高;PH3净化效率随催化剂用量增大而提高。在优化后的实验条件下,考察催化剂以CO为载气时催化剂对PH3的净化效率,虽然净化效果比以N2为载气时差,但反应较稳定,持续时间较长,有较好的抗杂毒性,且催化剂具有再生性能。     

Estimation of source locations of total gaseous mercury measured in New York State using trajectory-based models

Ambient gaseous phase mercury concentrations (TGM) were measured at three locations in NY State including Potsdam, Stockton, and Sterling from May 2000 to March 2005. Using these data, three hybrid receptor models incorporating backward trajectories were used to identify source areas for TGM. The models used were potential source contribution function (PSCF), residence time weighted concentration (RTWC), and simplified quantitative transport bias analysis (SQTBA). Each model was applied using multi-site measurements to resolve the locations of important mercury sources for New York State.PSCF results showed that southeastern New York, Ohio, Indiana, Tennessee, Louisiana, and Virginia were important TGM source areas for these sites. RTWC identified Canadian sources including the metal production facilities in Ontario and Quebec, but US regional sources including the Ohio River Valley were also resolved. Sources in southeastern NY, Massachusetts, western Pennsylvania, Indiana, and northern Illinois were identified to be significant by SQTBA. The three modeling results were combined to locate the most important probable source locations, and those are Ohio, Indiana, Illinois, and Wisconsin. The Atlantic Ocean was suggested to be a possible source as well.     

Life-cycle phases of a zinc- and cadmium-resistant ecotype of Silene vulgaris in risk assessment of polymetallic mine soils

Short-term exposure of plants to heavy metals is often used for risk assessment of metal-enriched soils (OECD guideline 208) without considering the reliability of the assessment for long-term exposure, i.e. for the completion of a plant's life-cycle. In the present study with 15 orogenic soils three phases of the life-cycle of a Zn-Cd-resistant ecotype of Silene vulgaris were studied to improve risk assessment of metal-enriched soils. The first phase, i.e. emergence of seedlings was not related to the water-soluble or total metal concentration of the soils. Seedling mortality was low as long as the water-soluble metal concentration did not surpass 0.15 micromol Zn and 0.04 micromol Cu g(-1) dry soil. Curtailment of the life-cycle prior to flowering, i.e. the vegetative growth as second phase, occurred on those soils where roots and shoots were heavily enriched by Zn already in the seedling phase. In the third phase, i.e. the generative phase, time to flowering and yield differences between orogenic soils were substantial, but soil metal concentrations could not be directly related to timing of reproduction or biomass. Ranking of data showed a high inconsistency of the responses to metal exposure during the first phases of the life-cycle. It is concluded that total plant mass and seed mass are the only realistic endpoints of life-cycle bioassays in risk assessment as long as ranks are inconsistent between two successive early phases of the life-cycle.     

Monitoring of heavy metal deposition in Northern Italy by moss analysis

A survey of heavy metal deposition in the mountainous territories of Northern Italy was carried out in 1995-96. Moss samples (mainly Hylocomium splendens) were collected in a dense network of sites (about 3.2 sites/1000 km(2)) and the data of metal concentrations in moss tissues were statistically correlated with environmental and climatic factors, as well as with bulk deposition of elements and elemental concentrations in the soil. Three main geographic patterns of metal concentration in mosses could be defined: (1) Fe, Ni, and Cr, all derived both by soil particulates and anthropogenic emissions connected with ferrous metal manufacturing, were mostly concentrated in Northwestern Italy; (2) Cu and Zn, as typical multi-source elements, showed rather high concentrations with little ranges of variation over the whole area and small peaks reflecting local source points; (3) Cd and Pb reflected long-distance transport and showed highest concentrations in the regions with highest precipitation, especially in the Eastern Alps.     

Anthropogenic magnetic particles and heavy metals in the road dust: Magnetic identification and its implications

Magnetic properties of road dusts in the East Lake area in Wuhan, China, were measured and compared with the results of heavy metal analyses in order to delineate the sources of pollutants. A total of ninety-seven dust samples were collected spatially from four segments with different traffic density and field settings from the roads encircling the lake. Thermomagnetic and hysteresis measurements revealed that the dominant magnetic carrier is coarse-grained magnetite. Correlations between magnetic parameters and element concentrations with traffic density and distances to the industrial region revealed that elements Cu, Ni and Fe mainly originate from vehicle traffic, which is also the major source of coarser magnetic particles (e.g., pseudo-single-domain/multi-domain (PSD/MD) grains), while element Pb and the smaller grains such as single-domain (SD) magnetic particles mainly originate from industrial emissions. The ratio between anhysteretic remanent magnetization and low-field magnetic susceptibility (ARM/χ_lf) can be employed as an indirect indicator for Cu, Fe and Ni emissions resulting from vehicle traffic. Due to the intermixture of elements from different sources, the element concentrations are not conclusive about the pollution source. A linear correlation between magnetic concentration-related parameters (e.g., ARM and saturation isothermal remanent magnetization, SIRM) and the concentrations of major elements (e.g., Cu, Co, Fe, Mn, Ni and V) suggests that they can be used as a proxy for heavy metal pollution. Road dusts in four segments show different magnetic characteristics, indicating various influxes of anthropogenic magnetic materials from vehicle traffic and industrial plants due to the different traffic loads and field settings. These results suggest that magnetic measurements can serve as an efficient complementary tool for the routinely employed geochemical methods to map the heavy metal pollution and trace the sources of pollutants in the road dust.     

Distribution,origin, and transformation of metal and metalloid pollution in vegetable fields,irrigation water,and aerosols near a Pb-Zn mine

Pollution of arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), and zinc (Zn) in vegetable fields was investigated near a Pb-Zn mine that has been exploited for over 50 years without a tailing reservoir. A total of 205 water, soil, and aerosol samples were taken and quantified by combined chemical, spectrometric, and mineral analytical methods. The pollution origins were identified by Pb isotopes and the pathways of transformation and transport of the elements and minerals was studied. The data showed that the vegetable fields were seriously polluted by As, Cd, and Pb. Some concentrations in the samples were beyond the regulatory levels and not suitable for agricultural activities. This study revealed that: (1) particulate matter is a major pollution source and an important carrier of mineral particles and pollutants; (2) the elements from the polluted water and soils were strongly correlated with each other; (3) Pb isotope ratios from the samples show that Pb minerals were the major pollution sources in the nearby vegetable fields, and the aerosols were the main carrier of mining pollution; (4) the alkaline, rich-carbonate, and wet conditions in this area promoted the weathering and transformation of galena into the secondary minerals, anglesite and cerussite, which are significant evidence of such processes; (5) the soil and the aerosols are a recycled secondary pollution source for each other when being re-suspended with wind. Highlights ? Mining activities generated heavy metal pollution in fields around a Pb-Zn mine ? The elements from water and soils are strongly correlated ? Anglesite and cerussite are evidence of galena transformation into secondary minerals ? Particulate matter is an important transport carrier of pollution     

Assessment of tin and butyltin species in estuarine superficial sediments from Gipuzkoa,Spain

Ten superficial sediments from river estuaries of Gipuzkoa (North Spain) were collected and analyzed for nine metals (including tin, Sn) and butyltin compounds (monobutyltin, MBT; dibutyltin, DBT; tributyltin, TBT). Total metal concentration in the fine fraction (<63 micrometer) of the sediment was determined in aqua regia--hydrofluoric acid extracts by atomic absorption spectrometry. The butyltin species (BTs) were firstly extracted from the sediments with hydrochloric acid-methanol mixture. After derivatization with sodium tetraethyl borate, the organotin compounds were extracted by solid phase microextraction (SPME) in headspace mode. A fiber coated with 100 micrometer poly(dimethylsiloxane) was used for SPME. The organotin species were analyzed by gas chromatography-flame ionization detection. Analysis of the certified reference sediment (PACS-2) shown the suitability of the procedures for determination of metal contents and DBT-TBT species in contaminated sediments. Factorial analysis was used to examine the main sources of metals. Three factors represented more than 89% of the total variance of the metal system, and the Sn was related with Cu-Zn-Pb suggesting the same pollution source. The BTs concentrations in the area were high (TBT ranged from 0.05 to 5.48 mg Sn kg(-1)). The percentage of total butyltin species ( summation operator BTs) respect to the total Sn amount was higher than 4% in all the sediments, showing in the Bidasoa river estuary a remarkable value higher than 20%. Hence, the studied estuarine sediments reflect a pollution that is related with historical industrial and fishing activities of the area.     

Selective catalytic oxidation of ammonia over copper-cerium composite catalyst

This work considers the oxidation of ammonia (NH3) by selective catalytic oxidation (SCO) over a copper (Cu)-cerium (Ce) composite catalyst at temperatures between 150 and 400 degrees C. A Cu-Ce composite catalyst was prepared by coprecipitation of copper nitrate and cerium nitrate at various molar concentrations. This study also considers how the concentration of influent NH3 (500-1000 ppm), the space velocity (72,000-110,000 hr(-1)), the relative humidity (12-18%) and the concentration of oxygen (4-20%) affect the operational stability and the capacity for removing NH3. The effects of the O2 and NH3 content of the carrier gas on the catalyst's reaction rate also are considered. The experimental results show that the extent of conversion of NH3 by SCO in the presence of the Cu-Ce composite catalyst was a function of the molar ratio. The NH3 was removed by oxidation in the absence of Cu-Ce composite catalyst, and approximately 99.2% NH3 reduction was achieved during catalytic oxidation over the Cu-Ce (6:4, molar/molar) catalyst at 400 degrees C with an O2 content of 4%. Moreover, the effect of the initial concentration and reaction temperature on the removal of NH3 in the gaseous phase was also monitored at a gas hourly space velocity of less than 92,000 hr(-1).     

Impact of microbial activity on copper, lead and nickel mobilization during the bioremediation of soil PAHs

A fungal bioremediation method using P. frequentans removed up to 75% of phenanthrene with the addition of water and nutrients over a period of 30 d. During the bioremediation process, changes in metal behavior were monitored by an in situ technique (diffusive gradients in thin-films, DGT) and by soil solution chemistry. DGT provided absolute data on fluxes from the solid phase to the DGT device and relative trends of concentrations of the most labile metal species. DGT response indicated that bioremediation increases metal mobilization from the solid phase. Filtration provided data on the concentrations of solution phase (<0.45 microm) metal. In all case, metal fluxes and concentrations significantly increased after the bioremediation process began. Fluxes increased from <0.1 pg cm(-2)s(-1) before bioremediation to between 0.2 and 0.5 pg cm(-2)s(-1) after bioremediation. Metal concentrations in the soils solution (filtration at 0.45 microm) increased from 2 to 10 microg l(-1) (Cu), 1-4 microgl(-1) (Pb) and from 40 to 140 microg l(-1) (Ni) after bioremediation. Although over a short time period, these data strongly indicated that there was remobilization of metal from solid to solution (and thus to the DGT device) directly due to the bioremediation process. Although the mechanism was not unambiguously identified, it was shown not to be related to small changes in bulk pH over time and was attributed to the microbial action on the surface of the soil solid phase, releasing metal into solution. Additionally, differences in metal concentration and flux were observed in sterilized and non-sterilized soils and in the absence or presence of phenanthrene. The results indicated that the bioremediation of soil by P. frequentans increased the flux, lability and mobility of trace metal species and therefore the likely metal bioavailability to plants.