重金属检测方法研究综述

重金属超标会造成环境污染,同时重金属在生物体内的积累效应会对人类的健康造成潜在地威胁.主要从应用新型的科技成果到结合生物技术对重金属的检测方法做一综述,以期为建立灵敏度更高、更准确、更快速的检测方法提供参考.     

Maternal transfer of brominated flame retardants in zebrafish (Danio rerio)

In many species reproduction and embryonic development have been shown to be sensitive to environmental contaminants. Understanding embryonic exposure to environmental contaminants is thus highly important. In this study concentrations of brominated flame retardants (BFRs) were measured in zebrafish eggs after parental exposure for 42 days via the diet. Zebrafish were exposed to two doses of eleven structurally-diverse BFRs. Eight BFRs were detected in the female zebrafish and maternal transfer to eggs was evident for all eight compounds. The highest concentrations in eggs were observed for hexabromocyclododecane (HBCD) and 2,4,4'-tribromodiphenyl ether (BDE 28), followed by 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE 183) and tetrabromobisphenol A 2,3-dibromopropyl ether (TBBPA DBPE). Five potential BFR metabolites were tentatively identified in female fish and maternal transfer was observed also for these compounds. The lipid adjusted concentrations in eggs were significantly higher than the concentrations in female fish for several of the BFRs. Further, the results showed a generally higher transfer in the lower exposure level and also indicated a dependency on the physico-chemical properties of the compounds.     

Spatial trends of polyfluorinated compounds in guillemot (Uria aalge) eggs from North-Western Europe

Polyfluorinated alkyl compounds (PFCs) are a group of chemicals of growing concern that have been detected in biological and abiotic samples worldwide. This study reports the concentrations of a suite of PFCs: perfluorooctyl sulfonate (PFOS), perfluorooctyl sulfonamide (PFOSA) and perfluorinated carboxylic acids (PFCAs) in guillemot (Uria aalge) eggs, collected in North-Western Europe, from Iceland, the Faroe Islands, Sweden and two locations in Norway. The highest concentrations of PFOS were found in samples from Sweden (mean 400 ng g(-1) wet weight (w.w.)), which were almost five times higher than concentrations found in Norwegian samples (mean 85 ng g(-1)w.w. from both sample sites). The concentrations found in Icelandic and Faroe samples were lowest (mean 16 and 15 ng g(-1)w.w., respectively). Only Swedish samples differed significantly from the other locations. In general, PFCAs show a different spatial trend than PFOS. Perfluorooctanoic acid (PFOA) was not detected in any sample and perfluorononanoic acid (PFNA) was only detected in samples from Sweden. The most abundant PFCA was perfluoroundecanoic acid (PFUA) with highest concentrations in samples from Sweden (mean 82 ng g(-1)w.w.), samples from the Faroe Islands had the second highest concentration (mean 57 ng g(-1)w.w.) and samples from Iceland and Norway had concentrations ranging between 18 and 30 ng g(-1)w.w. The original hypothesis was based on the idea that PFC concentrations are the highest close to more densely populated and industrialized areas and lower levels in remote areas. However, the geographic pattern is more complicated than predicted and varies among different PFCs.     

The effect of nitroaromatics' composition on their toxicity in vivo: novel, efficient non-additive 1D QSAR analysis

Novel 1D QSAR approach that allows analysis of non-additive effects of molecular fragments on toxicity has been proposed. Twenty-eight nitroaromatic compounds including some well-known explosives have been chosen for this study. The 50% lethal dose concentration for rats (LD50) was used as the estimation of toxicity in vivo to develop 1D QSAR models on the framework of Simplex representation of molecular structure. The results of 1D QSAR analysis show that even the information about the composition of molecules provides the main trends of toxicity changes. The necessity of consideration of substituents' mutual impacts for the development of adequate QSAR models of nitroaromatics' toxicity was demonstrated. Statistic characteristics for all the developed partial least squares QSAR models, except the additive ones are quite satisfactory (R2=0.81-0.92; Q2=0.64-0.83; R2 test=0.84-0.87). A successful performance of such models is due to their non-additivity i.e. possibility of taking into account the mutual influence of substituents in benzene ring which plays the governing role for toxicity change and could be mediated through the different C-H fragments of the ring. The correspondence between observed and predicted by these models toxicity values is good. This allowing combine advantages of such approaches and develop adequate consensus model that can be used as a toxicity virtual screening tool.     

Influence of gas flow-induced shear stress on the operation of the Anammox process in a SBR

The start up and performance of the Anammox process were tested in sequencing batch reactors with two different configurations: a bubble column (SBR-B) and a gas-lift reactor (SBR-G). Different off-gas upflow velocities were tested (3.53-12.3 cm min(-1)) in order to expose the biomass to different shear conditions and to study their effects on both efficiency and physical properties of the Anammox granular biomass. For the SBR-B the minimum gas upflow velocity needed to achieve biomass suspension inside the reactor was 12.3 cm min(-1). Such velocity made impossible the stable operation of the process. The fluidization of biomass for the SBR-G was reached at a gas upflow velocity of 3.52 cm min(-1). This system maintained an efficiency of nitrite removal around 98% at values up to 5.29 cm min(-1) but when the gas upflow velocity was increased from 5.29 to 9.70 cm min(-1) a significant decrease of the specific Anammox activity of the biomass from 0.35 to 0.05 g Ng(-1) VSS d(-1) was measured. The system lost 85% of its nitrogen removal efficiency which was not restored in spite of returning the gas upflow velocity to its initial value.     

Semipermeable membrane device (SPMD) for monitoring PCDD and PCDF levels from a paper mill effluent in the Androscoggin River, Maine, USA

Paper mill effluents may contain polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) that are normally generated due to chlorinated bleaching of pulp and paper. We used the semipermeable membrane device (SPMD) to monitor PCDD/F levels upstream and downstream of a paper mill on the Androscoggin River, in Jay (ME). Following the 36 day deployment, SPMD dialysis and cleanup, the samples were analyzed by HRGC/HRMS. Total concentrations of PCDD/Fs in SPMDs (sum of all tetra-through octachlorinated congeners) ranged from 4.71 pg g(-1) to 26.26 pg g(-1). Five out of the targeted 17 toxic congeners were detected, including: 2,3,7,8-TCDF; 1,2,3,7,8-PeCDF; 2,3,4,7,8-PeCDF; 1,2,3,4,6,7,8-HpCDD and OCDD. Permeability reference compounds (PRCs) were used for in situ calibration of the SPMD sampling rate (Rs). In all sites, water concentrations were the highest for OCDD (0.081-0.103 pg l(-1)), and the lowest for 1,2,3,7,8-PeCDF (0.005-0.009 pg l(-1)). There was not a consistent pattern of upstream-downstream gradient in the PCDD/F levels. This suggested that processes other than the mill in Jay (multiple sources, river dynamics) governed the flux of PCDD/Fs in the sampling locations. The SPMD results were validated by comparison to other studies on the Androscoggin River and elsewhere, confirming the potential of the device as a useful monitoring technique for PCDD/Fs in large river systems.     

Photocatalytic and combined anaerobic-photocatalytic treatment of textile dyes

A photocatalytic process based on immobilized titanium dioxide was used to treat crude solutions of azo, anthraquinone and phthalocyanine textile dyes. In addition, the process was applied to the treat autoxidized chemically reduced azo dyes, i.e. representatives of recalcitrant dye residues after biological sequential anaerobic-aerobic treatment. Photocatalysis was able to remove more than 90% color from crude as well as autoxidized chemically reduced dye solutions. UV-absorbance and COD were also removed but to a lower extent (50% in average). The end products of photocatalytic treatment were not toxic toward methanogenic bacteria. The results demonstrate that photocatalysis can be used as a pre- or post-treatment method to biological anaerobic treatment of dye-containing textile wastewater.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.     

Mechanical Property Characterization of Plasticized Sugar Beet Pulp and Poly(Lactic Acid) Green Composites Using Acoustic Emission and Confocal Microscopy

Sorbitol and glycerol were used to plasticize sugar beet pulp-poly(lactic acid) green composites. The plasticizer was incorporated into sugar beet pulp (SBP) at 0%, 10%, 20%, 30% and 40% w/w at low temperature and shear and then compounded with poly(lactic acid) (PLA) using twin-screw extrusion and injection molding. The SBP:PLA ratio was maintained at 30:70. As expected, tensile strength decreased by 25% and the elongation increased. Acoustic emission (AE) showed correlated debonding and fracture mechanisms for up to 20% w/w plasticizer and uncorrelated debonding and fracture for 30–40% sorbitol and 30% glycerol content in SBP–PLA composites. All samples had a well dispersed SBP phase with some aggregation in the PLA matrix. However, at 40% glycerol plasticized SBP–PLA composites exhibited unique AE behavior and confocal microscopy revealed the plasticized SBP and PLA formed a co-continuous two phase system.

Assessment of sediment contamination in Casco Bay, Maine, USA

The current status of contaminant concentrations in Casco Bay, decadal trends of these contaminants and changes in their geographical distribution are assessed using sediment samples collected approximately 10 years apart. In general, regulated contaminants appeared to be decreasing in concentration. Total PAH and dioxins/furans concentrations did not significantly change over this period. Total organochlorine pesticides, 4,4-DDE, 4,4-DDD, total DDT, PCB, tributyltin and total butyltin decreased in concentration. Trace element concentrations in sediments decreased at the majority of the sampling sites for chromium, nickel, and selenium while arsenic, cadmium, copper, lead, mercury, silver, and zinc remained relatively constant. None of the contaminants measured has increased by more than a factor of 2. Selected sites located in the Inner Bay, where concentrations are higher and new inputs were more likely, showed increased concentrations of contaminants. Most contaminants were not found at concentrations expected to adversely affect sediment biota based on ERL/ERM guidelines.