Stable metal isotopes reveal copper accumulation and loss dynamics in the freshwater bivalve Corbicula

Characterization of uptake and loss dynamics is critical to understanding risks associated with contaminant exposure in aquatic animals. Dynamics are especially important in addressing questions such as why coexisting species in nature accumulate different levels of a contaminant. Here we manipulated copper (Cu) stable isotopic ratios (as an alternative to radioisotopes) to describe for the first time Cu dynamics in a freshwater invertebrate, the bivalve Corbicula fluminea. In the laboratory, Corbicula uptake and loss rate constants were determined from an environmentally realistic waterborne exposure to 65Cu (5.7 microg L(-1)). That is, we spiked deionized water with Cu that was 99.4% 65Cu. Net tracer uptake was detectable after 1 day and strongly evident after 4 days. Thus, short-term exposures necessary to determine uptake dynamics are feasible with stable isotopes of Cu. In Corbicula, 65Cu depuration was biphasic. An unusually low rate constant of loss (0.0038 d(-1)) characterized the slow component of efflux, explaining why Corbicula strongly accumulates copper in nature. We incorporated our estimates of rate constants for dissolved 65Cu uptake and physiological efflux into a bioaccumulation model and showed that dietary exposure to Cu is likely an important bioaccumulation pathway for Corbicula.     

Comparative studies on trace metal levels in marine biota

Summary In whole krill, krill muscle tissue, krill products and in fillets of the antarctic fishNotothenia rossi marmorata, Dissostichus eleginoides, andNotothenia gibberifrons the levels of Cd, Pb, Cu, Ni, Hg and As have been determined. The methods applied were electrothermal AAS for Cd, Pb, Cu, and Ni, cold-vapour and hydride-generation AAS for Hg- and As, respectively, usually after HNO, pressure decomposition and for As followed by a HClO₄/H₂SO₄ treatment. Quality control was performed by analysis of appropriate Standard Reference Materials and working standards and by intercomparison with differential pulse anodicstripping voltammetry (DPASV) for Pb and Cd. The mean values obtained related to fresh weight for krill muscle meat (46 ng Cd/g, 50 ng Pb/g, 380 ng Cu/g, 130 ng Ni/g, 20 ng Hg/g, and 340 ng As/g) and fillets of antarctic fish ( ng Cd/g, 100 ng/Pb/g, 200 ng Cu/g, 150 ng Ni/g, 50 ng Hg/g, and 300-1500 ng As/g) confirm the absence of toxic risks for human food according to the present knowledge. Due to the somewhat higher, but not excessive, trace metal contents of krill products, these should be more suitable as a protein rich animal feed.

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Vergleichende Studien zum Spurenmetallgehalt in marinen BiotaII. Spurenmetalle in Krill, Krillprodukten und Fischen aus der antarktischen Scotia-See

Zusammenfassung In Rohkrill, Krillfleisch, Krillprodukten und in Filets der antarktischen FischeNotothenia Rossi Marmorata, Dissostichus Eleginoides undNotothenia Gibberifrons wurden die Gehalte an Cd, Pb, Cu, Ni, Hg und As bestimmt. Als Methoden wurden elektrothermale AAS für, Pb, Cu und Ni, Kaltdampf-bzw. Hydridtechniken für Hg und As nach HNO₃-Druckaufschluß, für gefolgt von einer Naßveraschung mit HCIO₄/H₂SO₄, eingesetzt. Die Qualitätskontrolle erfolgte durch die gleichzeitige Analyse geeigneter Standardreferenzmaterialien und Arbeitsstandards sowie durch Vergleich mit der differentiellen Pulsinversvoltammetrie (DPASV) füb und Cd. Die erhaltenen, auf Frischgewicht bezogenen, Mittelwerte für Krillfleisch (46 ng Cd/g; 50 ng Pb/g; 380 ng Cu/g; 130 ng Ni/g; 20 ng Hg/g und 340 ng As/g) und im Filet antarktischer Fische ( 3 ng Cd/g; 100 ng Pb/g; 200 ng Cu/g; 150 ng Ni/g; 50 ng Hg/g und 300-1500 ng As/g) bestätigen nach derzeitigem Kenntnisstand deren toxische Unbedenklichkeit für die menschliche Ernährung. Aufgrund höherer, aber nicht exzessiver Spurenmetallgehalte der Krillprodukte durften sich diese eher als proteinreiches Tierfutter eignen.

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Reference [37] constitutes part I of thin series, references [8] and [38] are parts III and IV, respectively     

Oceanic biogeochemical controls on global dynamics of persistent organic pollutants

Understanding and quantifying the global dynamics and sinks of persistent organic pollutants (POPs) is important to assess their environmental impact and fate. Air-surface exchange processes, where temperature plays a central role in controlling volatilization and deposition, are of key importance in controlling global POP dynamics. The present study is an assessment of the role of oceanic biogeochemical processes, notably phytoplankton uptake and vertical fluxes of particles, on the global dynamics of POPs. Field measurements of atmospheric polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins (PCDDs), and furans (PCDFs) are combined with remote sensing estimations of oceanic temperature, wind speed, and chlorophyll, to model the interactions between air-water exchange, phytoplankton uptake, and export of organic matter and POPs out of the mixed surface ocean layer. Deposition is enhanced in the mid-high latitudes and is driven by sinking marine particulate matter, rather than by a cold condensation effect. However, the relative contribution of the biological pump is a function of the physical-chemical properties of POPs. It is concluded that oceanic biogeochemical processes play a critical role in controlling the global dynamics and the ultimate sink of POPs.     

Chemometric evaluation of trace metal concentrations in some nuts and seeds

Seventeen trace metals in acid digests of nuts and seeds were determined using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry. The data were subjected to chemometric evaluation using principal component analysis (PCA), linear discriminant analysis (LDA) and cluster analysis (CA) in an attempt to classify the samples. Hazelnuts (raw and dry roasted), almonds (raw and dry roasted), sunflower seeds (black and white), peanuts (raw and dry roasted), cashew nuts, Brazil nuts, walnuts, chickpeas (raw and dry roasted), pumpkin seeds (raw and dry roasted), and pistachio nuts were used as samples. The samples were classified into seven groups by PCA and CA. All group members determined using PCA and CA were found by LDA to be correctly classified in the predicted groups. Interestingly, the chemometric evaluation indicated that the raw and roasted nuts are very close to each other even though some originated from different countries.     

Mineral and trace metal levels in some cheese collected from Turkey

Concentrations of elements (Fe, Mn, Zn, Cu, Pb, Cr, Ni, Na, K, Ca and Mg) in cheese samples were analyzed using flame and graphite furnace atomic absorption spectrometry after microwave digestion. The order of levels of the elements in the samples was determined to be Na > Ca > K > Mg > Zn > Fe > Pb > Mn > Cr > Ni. The concentration ranges in the samples were found to be 4.1–12.5, 0.28–1.1, 8.8–13.2, 0.10–0.27, 0.14,–1.2, 0.02–0.62, 0.18–0.34, 3957–6558, 305–362, 3473–4556 and 28.9–127 μg/g for iron, manganese, zinc, copper, lead, chromium, nickel, sodium, potassium, calcium and magnesium, respectively. High trace metal and mineral accumulation levels in the samples were found in Van otlu cheese for Fe, Ordu çerkez cheese for Na, Kayseri çömlek cheese for Mn, Pb, Çeçil cheese for Zn, Kars ka?ar cheese for Cu, Cr, Tokat cheese for Ni, Ca and Erzincan tulum cheese for K, Mg, respectively.     

Chemometric approach to evaluate trace metal concentrations in some spices and herbs

Herbs (mint, thyme and rosemary) and spices (black pepper, chili pepper, cinnamon, cumin, sweet red pepper and turmeric) were analysed using atomic spectrometry and then subjected to chemometric evaluation in an attempt to classify them using their trace metallic analyte concentrations (As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Sr and Zn). Trace metals in acid digests of these materials were determined using both inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry. The chemometric techniques of principal component analysis (PCA), linear discriminant analysis (LDA) and cluster analysis (CA) were used for the classification studies. These herbs and spices were classified into five groups by PCA and CA. When the results of these techniques were compared with those from LDA, it was found that all group members determined by PCA and CA are in the predicted group that 100.0% of original grouped cases correctly classified by LDA.     

Biological and health implications of toxic heavy metal and essential trace element interactions

Human civilization and a concomitant increase in industrial activity has gradually redistributed many toxic metals from the earth's crust to the environment and increased the possibility of human exposure. Among the various toxic elements, heavy metals cadmium, lead, and mercury are specially prevalent in nature due to their high industrial use. These metals serve no biological function and their presence in tissues reflects contact of the organism with its environment. They are cumulative poison, and are toxic even at low dose. Studies of metabolism and toxicity of these elements have revealed important interactions between them and some essential dietary elements like calcium, zinc, iron, selenium, copper, chromium, and manganese. In general, a deficiency of these essential elements increases toxicity of heavy metals, whereas an excess appears to be protective. While most of the observations are on laboratory animals, limited human data are in agreement with the results of animal experiments. These suggest that the dietary presence of the essential elements may contribute to the protection of man and animal from the effects of heavy metal exposure, while their deficiency may increase toxicity. Appropriate dietary manipulation thus may be valuable in the prevention and treatment of heavy metal toxicity.     

Cadmium exposure and phosphorus limitation increases metal content in the freshwater alga Chlamydomonas reinhardtii

The characteristics of metal accumulation in freshwater microalgae are important to elucidate for a full understanding of metal cycling and toxicity in a freshwater system. This study has utilized an elemental profiling approach to investigate the impacts of Cd exposure and phosphorus (P) availability on metal accumulation after 7 days in batch culture-grown Chlamydomonas reinhardtii. Multivariate statistical analysis of the elemental data demonstrated distinct responses between both stresses. Sublethal concentrations of Cd (up to 15 μM) caused increased accumulation of Co. Cu, Fe, and Zn content also increased in response to enhanced Cd concentrations but only when P availability was low. While Cd exposure effected the accumulation of a few specific metals, P limitation increased the accumulation of all essential trace metals and macronutrients analyzed including Co, Fe, K, Na, and Zn but not Mn. The accumulation of Cd also markedly increased in response to P limitation. The impact of P availability on essential metal accumulation was the same when either inorganic P or an organic P source (glycerophosphate) was used. These results highlight the potential risks of metal toxicity for freshwater microalgae and aquatic food chains when P availability is limiting and which can be exacerbated by Cd pollution.     

Interpretation of in situ speciation measurements of inorganic and organically complexed trace metals in freshwater by DGT

The dynamic speciation technique, diffusive gradients in thin-films (DGT), has been used in freshwater to determine simultaneously, from a single set of in situ measurements, (1) the equilibrium distribution of metal ions between simple inorganic complexes and larger organic complexes and (2) information on the rates of dissociation of these complexes. DGT devices with different diffusion layer thicknesses (0.3, 0.54, 1.34, and 2.14 mm) were used to estimate the in situ dissociation kinetics. Information on the species distribution was obtained by using two types of gel, which allow relatively free (polyacrylamide, APA) and more retarded (restricted, RES) diffusion of the metal complexes. The full theoretical basis of the technique is developed and applied to in situ measurements of Mn, Fe, Co, Ni, Cu, Cd, and Pb in a pristine river (Wyre, U.K.), with high DOC(15mg L(-1)), assuming that organic complexes are dominated by fulvic acid. These first DGT measurements that do not rely on assumptions about complex lability or the distribution of species, are compared to total dissolved measurements, previously reported speciation calculations and measurements using alternative speciation techniques. Examination of calculation consistency suggests that the effective mean diffusion coefficients of metal complexes with organic matter under in situ conditions may be larger than those measured in the laboratory using extracted fulvic acid.     

Measurement and dynamic modeling of trace metal mobilization in soils using DGT and DIFS

The technique of diffusive gradients in thin-films (DGT) accumulates metals on a Chelex resin after their diffusive transport through a hydrogel. It lowers metal concentrations in soil solution adjacent to the device and induces resupply of metal associated with the solid phase. DGT devices were deployed in an alluvial gley soil for 21 different time periods between 4 h and 19.5 d. The accumulated masses of Cu, Cd, Ni, and Zn were used to calculate the distribution coefficient for labile metal, Kdl, and adsorption and desorption rate constants. Calculations were performed using a dynamic numerical model of DGT-induced fluxes in soils (DIFS). It assumes first-order exchange between solid phase and solution and diffusional transport in both the soil solution and the hydrogel. The DIFS model fitted changes in accumulated mass with time very well. Values of Kdl calculated from DIFS of 100 (Cd), 250 (Cu), 150 (Ni), and 150 (Zn) were larger than values of distribution coefficients estimated by exchange with Ca(NO3)2 but similar to those estimated by isotopic exchange (Cd and Zn only). These results suggest that the solid-phase pool of metal affected by the removal of labile metal by DGT, which operates on a time scale of minutes, is similar to the solid-phase pool of metal that can isotopically exchange with solution on a time scale of 2 d. Response times of minutes were consistent with interaction rates with surfaces, and desorption rate constants agreed with other reported values. An appraisal of the DIFS model demonstrated the importance of the labile pool size in the solid phase for controlling supply to a sink, such as DGT or a plant. As values of Kdl and kinetic parameters are obtained using DGT with minimal soil disturbance and by a similar mechanism to that involved in plant uptake, they may be pertinent to bioavailability studies.     

食品重金属快速检测仪测量大米中痕量镉的长期稳定性研究

通过对397台食品重金属检测仪测量大米中镉的长期稳定性测量数据进行统计,引入系统评价方法研究仪器在相应时段内的检验重复性、检验时段间的总精密度及总平均值的正确度.大米标准样品GBW(E)100348中镉的总平均值在认定值±5％ 区间内波动,统计发现,时段内相对标准偏差≤15％ 的仪器占98.5％,长期稳定性满足精密度要...     

用于聚酰胺纺织品的金属络合染料和化学品之间的人体生态相关性

报道了金属络合染料染色的聚酰胺纺织品中减少Cr（Ⅲ）释放的原因和可能性。确定了在金属络合染料染色的聚酰胺织物上,常常可观察到与通常的生态标签相关的Cr（Ⅲ）超出限量的现象,这首先可跟踪到整理制,尤其是通过浸轧施加的,描述了铬固定的可能性。因此．这种面向应用的研究工作在整理工厂首先是与操作工密切相关联的,而没有更直接地审察它们之间的化学关系。     

Numerical approach to speciation and estimation of parameters used in modeling trace metal bioavailability

Speciation affects trace metal bioavailability. One model used to describe the importance of speciation is the biotic ligand model (BLM), wherein the competition of inorganic and organic ligands with a biotic ligand for free-ion trace metal determines the ultimate metal availability to biota. This and similar models require natural ligand concentrations and conditional stability constants as input parameters. In concept, the BLM is itself an analogue of some analytical approaches to the determination of trace metal speciation. A notable example is competitive ligand equilibration/cathodic stripping voltammetry, which employs an artificial ligand for comparative assessment of natural ligand concentrations and discrete conditional stability constants (i.e., BLM parameters) in a natural sample. Here, we report a new numerical approach to voltammetric speciation and parameter estimation that employs multiple analytical windows and a two-step optimization process, simultaneously generating both parameters and a complete suite of corresponding species concentrations. This approach is more powerful, systematic, and flexible than those previously reported.     

Biofilm hydrous manganese oxyhydroxides and metal dynamics in acid rock drainage

Biofilms in shallow, tailings-associated acid rock drainage (ARD) accumulated metals from May to September, indicating scavenging is stable within these biological solids over seasonal time frames. Results indicate a doubling (Mn, Cr) to over a 6-fold increase (Ni, Co) in biofilm metal concentrations. Biofilm oxygen and pH gradients measured over diel time scales with microelectrodes were observed to be both spatially and temporally variable, indicating that biofilms are highly dynamic geochemical environments. Biofilm metal retention and affinities were element specific indicating different processes control their sequestration. Metals were specifically scavenged by the organic constituents of the biofilm itself (Ni, Co) and associated biominerals of amorphous Mn oxyhydroxides (HMO; Ni, Co, and Cr). Results are consistent with sorption and coprecipitation processes controlling Ni and Co biofilm association, while Cr dynamics appear linked to those of Mn through redox processes. Biofilm HMO concentrations increased seasonally but showed significant diel fluctuations, indicating that both formation and dissolution processes occurred over rapid time scales in these biofilms. Biofilm HMO concentrations increased nocturnally but decreased during daylight hours to late afternoon minima. Under the geochemical conditions of the streams, observed HMO formation rates can only be explained by microbial catalysis. These results are the first to quantitatively examine microbial biofilm metal dynamics using microscale, geochemical techniques at both diel and seasonal time scales. They provide strong evidence for the significant role that microbial activity can play in metal geochemistry in natural environments.     

Reduction of 2,4,6-trinitrotoluene by iron metal: kinetic controls on product distributions in batch experiments

The reaction kinetics and product distributions for the reduction of 2,4,6-trinitrotoluene (TNT) by granular iron metal (Fe0) were studied in batch experiments under a variety of initial concentrations of TNT and Fe0. Although the kinetics of TNT disappearance were found to behave in accord with the standard theory for surface-mediated reactions, a complex relationship was found between the initial concentrations of TNT and Fe0 and the appearance of the expected nitro reduction product, 2,4,6-triaminotoluene (TAT). TNT was completely converted to TAT only when the initial concentration of TNT was low and/or the initial concentration of Fe0 was high. Mathematical analysis of a range of generic reaction schemes that produce stable end products in addition to TAT showed that (i) surface complexation of TAT is insufficient to describe all of our data and (ii) polymerization reactions involving TAT and/or various reaction intermediates are the likely source of the incomplete conversion of TNT to TAT at high initial TNT concentration and low Fe0 concentration. The relationship between TAT production and reaction conditions is shown to imply that passivation due to reaction products is more likely when the ratio of initial TNT concentration to Fe0 concentration is high and, therefore, that passivation rates observed at the laboratory scale are likely to be faster than those which would be observed at the field scale.     

Influence of metal speciation in natural freshwater on bioaccumulation of copper and zinc in periphyton: a microcosm study

The free ion activity model (FIAM) has already been confirmed under laboratory conditions for many trace metals but has still to be validated under natural conditions where the presence of natural organic ligands influences metal speciation and bioavailability. The goal of this study was to test if the FIAM is followed under natural conditions by measuring copper and zinc speciation as well as metal accumulation in periphyton. Periphyton was exposed in microcosms to natural river water with different added concentrations of copper (25-258 nM) or zinc (18-501 nM) and additions of a synthetic ligand (NTA). Free Cu2+ was in the range of 10(-16.5)-10(-14.5) M and Zn(2+) was in the range of 0.7-8.7 nM, as measured by competitive ligand exchange coupled with cathodic/anodic stripping voltammetry. Other metal complexes were either measured or computed. Bioaccumulation of zinc in periphyton appeared to be controlled by the free zinc ion concentration, confirming the FIAM. In contrast, bioaccumulation of copper was controlled by weakly complexed copper (including Cu2+ plus inorganic and weak organic complexes), which is in disagreement with the FIAM, and appears to be caused by limitation of copper diffusion due to very low free Cu2+ occurring in natural environments.     

3种养殖淡水鱼重金属含量测定及健康风险评价

目的 了解福建省主要养殖淡水鱼中重金属含量水平及进行鱼类食用安全性评价,为福建省淡水鱼健康养殖和食用安全性提供参考依据。方法 选择草鱼、罗非鱼和鳗鱼为研究对象,测定和分析其重金属含量,运用单因子污染指数法、综合污染指数法和目标危险系数法进行污染评价。结果 3种养殖淡水鱼肌肉中重金属含量最高的是Cr。Cd与Pb和Hg呈极显著相关,与As呈极显著负相关;Cr与Hg呈显著负相关;Hg与As呈极显著负相关。5种重金属均未出现超标现象,草鱼受到As轻度污染、罗非鱼受到Pb和As轻度污染、鳗鱼受到Cd和Pb轻度污染,但3种淡水鱼未受到综合污染。结论 食用该批次生产的草鱼、罗非鱼和鳗鱼不存在潜在健康风险,今后应继续保持高压监管,并对出现的个别重金属的污染风险进行更精准的管控。     

Impact of natural organic matter on floc size and structure effects in membrane filtration

Hematite (10 mg of Fe/L) floc-humic acid assemblages have been formed at pH 4 either by first aggregating hematite particles with salt (100 mM KCl) and then adding humic acid (salt-particle-organic or SPO assemblages) or by suspending the hematite particles in humic acid solutions and then adding salt to induce aggregation (organic-particle-salt or OPS assemblages). The behavior of these assemblages upon deposition on microfiltration (MF) membranes has then been investigated. In the OPS case, the fractal dimension (dF) of the assemblages formed varied dramatically depending upon the extent of charge neutralization by added fulvic acid with dF values typical of diffusion-limited cluster aggregates at low (0.1-0.2 mg/L) humic acid concentrations and dF values typical of reaction-limited cluster aggregates either in the absence of humic acid or concentrations greater than 0.4-0.6 mg/L. In the SPO case, dF values on the order of 2.1 were initially observed and were found to decrease to around 1.8-1.9 for humic acid concentrations greater than 0.6-0.8 mg/L. OPS assemblages with low fractal dimensions were found to be highly compressible once deposited on MF membranes with significantly higher specific cake resistances than was the case for SPO assemblages at transmembrane pressures of 50 kPa and above. These results highlight the importance of both the choice of coagulant (e.g., preformed vs formed in situ) and the transmembrane pressure to which a membrane filtration process might be allowed to rise prior to removal of the fouling layer.     

Evaluation of trace metal concentrations in some herbs and herbal teas by principal component analysis

Sixteen trace metallic analytes (Ba, Ca, Ce, Co, Cr, Cu, Fe, K, La, Mg, Mn, Na, Ni, P, Sr and Zn) in acid digests of herbal teas were determined and the data subjected to chemometric evaluation in an attempt to classify the herbal tea samples. Nettle, Senna, Camomile, Peppermint, Lemon Balm, Sage, Hollyhock, Linden, Lavender, Blackberry, Ginger, Galangal, Cinnamon, Green tea, Black tea, Rosehip, Thyme and Rose were used as plant materials in this study. Trace metals in these plants were determined by using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry. Principal component analysis (PCA), linear discriminant analysis (LDA) and cluster analysis (CA) were used as classification techniques. About 18 plants were classified into 5 groups by PCA and all group members determined by PCA are in the predicted group that 100.0% of original grouped cases correctly classified by LDA. Very similar grouping was obtained using CA.