Occurrence of polybrominated diphenyl ethers in fish and shellfish downstream from electronic-waste recycling plants

We measured 39 polybrominated diphenyl ethers （PBDEs） in the muscle tissue of three species of fish （Sciaenops ocellatus,Sparus macrocephalus,and Lateolabrax japonicus） and four species of shellfish （Tegillarca granosa,Cyclina sinensis,Sinonovacula constricta,and Ostrea cucullata） that were collected downstream of electronic-waste recycling plants in Taizhou,China.A total of 24 PBDE congeners （PBDE 24） in the samples were detected.The PBDE 24 （total PBDE） ranged from 545.4 to 1688.7 ng/kg ww （wet weight）.The mean PBDE 24 concentration was 1382.6 ng/kg ww in fish and 858.1 ng/kg ww in shellfish.The lower brominated congeners were detected at relatively high concentrations in all species.The penta-products,produced from e-waste,were found at relatively low levels.A principal component analysis suggested a significant correlation among di-,tri-,tetra-,and hepta-BDEs for the three species of fish.Similarly,we found a significant correlation between mono-and tri-BDEs in the shellfish.Our results suggested that the processes of PBDE metabolism and elimination were similar in both fish and shellfish.In addition,the primary source of PBDEs appeared to be from the debromination of high brominated PBDEs.

Feasibility of Trace Alcohol Congener Detection and Identification Using Laser-Induced Breakdown Spectroscopy

In this paper, a feasible scheme is reported for the detection and identification of trace alcohol congeners that have identical elemental composition using laser-induced breakdown spectroscopy （LIBS）. In the scheme, an intensive pulsed laser is used to break down trace alcohol samples and the optical emission spectra of the induced plasma are collected for the detection and identifq ication of alcohol molecules. In order to prepare trace alcohol samples, pure ethanol or methanol is bubbled by argon carrier gas and then mixed into matrix gases. The key issue for the scheme is to constitute indices from the LIBS data of the alcohol samples. Two indices are found to be suitable for alcohol detection and identification. One is the emission intensity ratio （denoted as H/C） of the hydrogen line （653.3 nm） to the carbon line （247.9 nm） for identification and the other is the ratio of the carbon line （as C/Ar） or the hydrogen line （as H/Ar） to the argon lines （866.7 nm） for quantitative detection. The calibration experiment result shows that the index H/C is specific for alcohol congeners while almost being independent of alcohol concentration. In detail, the H/C keeps a specific constant of 34 and 23 respectively for ethanol and methanol. In the meanwhile, the C/Ar and H/Ar indices respond almost linearly to the alcohol concentration below 1300 ppm, and are therefore competent for concentration measurement. With the indices, trace alcohol concentration measurement achieves a limit of 140 ppm using a laser pulse energy of 300 mJ.

Incidents with Dioxins and PCBs in Food and Feed-Investigative Work, Risk Management and Economic Consequences

The identification of contamination sources within the food chain with polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs), (“dioxins”), and PCBs is difficult and complex. PCDD/PCDF can be formed as unintentional compounds in a number of chemical processes as well as in almost every combustion process. PCBs were intentionally produced chemicals that were manufactured for decades before the ban in marketing and use in many countries around 1985. The pattern of occurrence can change from the original source in particular via feedingstuffs to food of animal origin as result of bioaccumulation. A number of examples illustrate the challenging detective work and key scientific aspects for identification of the sources, for support of the risk management and for performance of monitoring programs. The contamination of milk and milk products in European countries with dioxins was caused by compound feeds containing citrus pulp pellets from Brazil which had high dioxin levels as a result of the use of heavily contaminated lime used for neutralization. The Belgian dioxin crisis was caused by a feed additive heavily contaminated with PCBs which were discharged into a recycled fat used in the production of animal feed. Guar gum from India was contaminated with sodium pentachlorophenate and dioxins. Clay was found to be possibly highly contaminated with dioxins possibly formed by geothermal processes over time;use of such clay as feed additive or for human intake led to elevated dioxin levels in food and humans. Bioanalytical screening in combination with comprehensive physicochemical investigations led to the detection of brominated flame retardants and brominated dioxins in a feed additive. Buffalo milk was contaminated in Italy presumably caused by illegal deposition of waste. High PCB levels in fuel oil for drying of breadcrumb used as a feed ingredient caused a major dioxin crisis with pork meat in Ireland. Fatty acids for technical purposes originating from a biodiesel company were used for production of feed fat which contaminated parts of the food chain in Germany. In addition to effects on human and animal health these incidents also have serious economic consequences which could be mitigated by more frequent control on food and feed. Addressing both these issues, the European Community has developed a strategy to reduce the presence of dioxins and PCBs in the environment and in feed and food comprising the establishment of maximum and action levels.

Preliminary Study towards Enhanced Crude Oil Biodegradation Reveals Congeneric Total Peroxidases with Striking Distinctions

Peroxidases (POXs) are the key extracellular enzymes produced by crude oil degrading microbes. Knowledge of optimum conditions for POXs activity is crucial for providing effective environment for bioremediation. In this study, physicochemical properties of POXs produced by Actinomyces israelii and Actinomyces viscosus during growth on crude oil were studied. The POXs exhibited similarities in activity and stability with striking differences in response to two divalent metal ions. The POXs from both species had optimum pH of 7.0 and were very stable over a narrow pH range (6.0 - 8.0). The POXs demonstrated similar thermostability exhibiting relative residual activity of 62% at 50°C after 30 min incubation and 45% residual activity at the same temperature after 60 min despite the fact that POXs from A. viscosus and A. israelii had optimum temperatures of 50°C and 40°C, respectively. The POXs from A. viscosus and A. israelii were greatly activated by Fe2+ at 5.0 and 10.0 mM. The enzymes were both strongly inhibited by Cu2+, Mg2+ and Hg2+. Surprisingly, these congeneric POXs demonstrated striking differences in their response to Ca2+ and Mn2+. POX from A. viscosus was activated by Ca2+ and Mn2+ exhibiting relative activity of 136% and 106% at 5 mM, respectively. In contrast, POX from A. israelii was strongly inhibited by Ca2+ and Mn2+ exhibiting 62.5% relative activity in the presence of 5 mM of each metal ion. Increasing the concentration of Ca2+ and Mn2+ led to further activation of POX from A. viscosus and inhibition of POX from A. israelii. Results provide deeper insights into functional properties of studied POXs from closely related microbes. The physicochemical properties are very similar;however, notable differences provide a strong basis for structural characterization of these congeneric enzymes.

Assessing the Potential Presence and Impact of Nile tilapia, Oreochromis niloticus (Pisces: Cichlidae;Linnaeus 1758) in Mutukutuku Reservoir in Solwezi, Zambia

Invasive alien species are one of the greatest threats to biodiversity and ecosystem globally,affecting delivery of ecosystem goods and services,and consequently human well-being.Oreochromis niloticus is one of the most highly successful invaders of aquatic ecosystems with competitive characteristic advantages over indigenous species.The aim of this study was to investigate the potential presence and impact of O.niloticus on Mitukutuku fishery.The study was undertaken using fisheries independent surveys for the period of 2 months.Fish identification key and gel electrophoresis identification methods were also used to confirm presence of O.niloticus and also possible hybridization with indigenous congeneric species.Fisheries dependent survey was conducted with fishers and traders to further assess presence of the invasive species and its impacts on their catches and socio-economic well-being.A total of 32 Oreochromis hybrids species and 19 of O.niloticus were found in the reservoir.This confirmed a higher proportion of O.niloticus in the reservoir.Results from interviews of fishers and traders revealed catch per unit effort of O.hybrids and O.niloticus to be higher compared to that of indigenous congeneric species.Similarly,fish traders confirmed that income for the fish sales increased from 5%in March to 7%in August.Overall,these results suggested that O.niloticus does not only exist in Mitukutuku reservoir,but also hybridizes with native species and dominates the entire stretch of the reservoir threatening loss of biodiversity and aquaculture breeding programme.There is need for restricting culture of O.niloticus in Zambia.

Comparison of PBDE congener profiles and concentration levels in human specimens from China and the US and identification of human exposure sources

In an effort to investigate the status of human exposure to PBDEs in China,available monitoring data in human specimens(including breast milk,serums,and blood) was collected from the general population as well as specific groups that are occupationally exposed.PBDEs exposure profiles and concentration levels were compared with their counterparts in the United States of America.It was found that PBDE burdens in general Chinese population are one order lower and have different congener profiles from that in the US,showing higher percentages of BDE-28 or BDE-153 in human specimens from China.Workers and residents in electronic wastes recycling regions or areas of commercial PBDE manufacturing have the highest PBDE exposure levels reported worldwide,which are close or higher than the exposure levels of the general population in the US. Highly brominated congeners,such as BDE-207 and 209,are among the major PBDE congeners,and BDE-209 has the highest percentage(above 50%) for all occupational populations studied.Principal components analysis(PCA) demonstrates that the exposure of the general population in the US is closely related to penta-BDE while the human burden in China is not.The PBDE in indoor air(gas phase) in the US is highly correlated with the PBDE burden in the general population in the US,indicating a major exposure pathway.For the occupationally exposed populations in China,the congener profiles are closely related to the commercial deca-BDE products.Examination of exposure profiles for general and occupational populations in China suggests that it is essential to include more highly brominated congeners,such as BDE-207 and 209,in future human exposure studies,in order to assess the real burdens and profiles of PBDEs exposure in China.Strict pollution prevention and occupational protection procedures are in need in China to avoid the PBDE contamination problem that has occurred in the US.

Gas-phase and particle-phase PCDD/F congener distributions in the flue gas from an iron ore sintering plant

The activated carbon injection-circulating fluidized bed（ACI-CFB）-bag filter coupling technique was studied in an iron ore sintering plant. For comparison, the removal efficiencies under the conditions without or with ACI technology were both evaluated. It was found that the polychlorinated dibenzo-p-dioxins and dibenzofuran（PCDD/F） removal efficiency for total international toxic equivalence quantity（I-TEQ） concentration was improved from 91.61% to 97.36% when ACI was employed, revealing that ACI was very conducive to further controlling the PCDD/F emissions. Detailed congener distributions of PCDD/Fs in the gas-phase and particle-phase of the Inlet and Outlet samples were determined. Additionally, the PCDD/F distribution for the Fly ash-with ACI sample of was also studied.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) emissions from electric arc furnaces for steelmaking

The proportion of steel produced using electric arc furnaces(EAFs)is increasing.In this study,polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs)concentrations and patterns in stack gas samples from three typical EAFs in steelmaking plants were determined to allow the contributions of EAFs in steelmaking plants to PCDD/Fs emissions in China to be assessed.Samples collection was accomplished by adopting the automatic isokinetic sampling technique,then the PCDD/Fs congeners concentrations were analyzed qualitatively and quantitatively by isotope dilution high-resolution gas chromatography high-resolution mass spectrometry(HRGC-HRMS).The mean PCDD/Fs mass concentrations in stack gases emitted during the scrap preheating phase of plants E1,E2,and E3 were 0.48,385.55,and 0.34 ng Nm^-3,respectively,and the total toxic equivalent(WHO2005-TEQ)concentrations were 0.05,33.16,and 0.03 ng Nm^-3,respectively.The PCDD/Fs mass concentration in stack gases emitted during the melting phase at plant E3 was 0.12 ng Nm^-3(0.02 ng WHO2005-TEQ Nm^-3).The operational temperature of the bag filter of the preheating in the E2 EAF was as high as 230℃,which is conducive to the generation of PCDD/Fs,whether the temperature in the bag filter of E1(150℃)and E3(120℃)are not.Moreover,the bag filter temperature is suggested to be best controlled to below 150℃.The emission factors(EF)for PCDD/Fs released into the air during the scrap preheating phase for plants E1,E2,and E3 were 0.13,52,and 0.10 mg WHO2005-TEQ t1,respectively,and the EF for the smelting phase from plant E3 was 0.14 mg WHO2005-TEQ t1.The emission factor in E2 is 5 times higher than the highest current UNEP toolkit factor for EAFs(10 mg TEQ/tonne steel).Therefore,an update for the UNEP toolkit emission factor for a few case plants is suggested.Several congeners,including 2,3,7,8-TeCDF,1,2,3,4,6,7,8-HpCDF,and 1,2,3,4,6,7,8-HpCDD,were dominant during the preheating phase,while 2,3,7,8-TeCDF,1,2,3,7,8-PeCDF,and 2,3,4,7,8-PeCDF were dominant during the smelting phase.The monitoring data from the case plants helps to better understand the PCDD/Fs emissions of EAFs using preheating process stages.However,a more complete emission inventory requires more case investigations on the PCDD/Fs emissions from representative EAFs steelmaking plants.

Influence of combustion-originated dioxins in atmospheric deposition on water quality of an urban river in Japan

Bulk（wet and dry） deposition samples were collected in Saitama Prefecture, Japan throughout a year（February 8, 2012 to February 7, 2013） to estimate the influence of dioxins emitting from waste incinerators on river water quality. The annual deposition flux of dioxins was 3.3 ng-toxic equivalent（TEQ）/m^2/year. Source identification using indicative congeners estimated that 82% of dioxin TEQ in the bulk deposition（2.7 ng-TEQ/m^2/year）was combustion-originated, indicating that most of the dioxins in the deposition were derived from waste incinerators. In Saitama prefecture the annual flux of combustionoriginated dioxins in depositions was apparently consistent with that of dioxin emission into the air from waste incinerators. The TEQ of combustion-originated dioxins in the deposition per rainfall was 2.4 pg-TEQ/L on annual average, exceeding the environmental quality standard（EQS） for water in Japan of 1 pg-TEQ/L. This suggests there is a possibility that dioxins in atmospheric deposition have a significant influence on the water quality of urban rivers which rainwater directly flows into because of many paved areas in the basins.The influence of combustion-originated dioxin in the deposition on the water quality of Ayase River, an urban river heavily polluted with dioxins, was estimated at 0.29 pg-TEQ/L on annual average in 2015. It seems that dioxins in atmospheric deposition from waste incinerators have a significant influence on water quality of some urban rivers via rainwater though the dioxins in the ambient air have achieved the EQS for atmosphere at all monitoring sites in Japan.