Brominated-chlorinated paraffins(Br-CPs)are a comparably new compound class that features both Cl and Br atoms on one or several alkane backbones.Due to legal restrictions in the use of conventional chlorinated paraff...Brominated-chlorinated paraffins(Br-CPs)are a comparably new compound class that features both Cl and Br atoms on one or several alkane backbones.Due to legal restrictions in the use of conventional chlorinated paraffins(CPs),Br-CPs have the potential to become emerging contaminants.Currently,their determination is hampered by the lack of suitable reference standards.Here,we present a simple synthesis procedure with single chain alkanes that leads to Br-CPs with∼4–8 chlorine and 1 to 4 bromine substituents according to gas chromatography with electron capture negative ion mass spectrometry(GC/ECNI-MS).The single-chain Br-CP mixtures were obtained by the shared chlorination and bromination of eight single-chain alkanes(C10 to C17)at two reaction times,respectively.The carbon content of the 16 single-chain Br-CP products,determined by elemental analysis(EA),ranged from 30.8 to 43.8%.The typical hump peak known from CPs was detected with GC with flame ionization detection(GC/FID),electron capture detection(GC/ECD)and GC/ECNI-MS.The complexity indicated that low-resolution mass spectrometry is not sufficient for an adequate analysis of Br-CPs.A mathematical formula was developed which allows to calculate all possible combinations of Br and Cl that are in line with the carbon content.The proton magnetic resonance spectroscopy(1H NMR)spectra showed similarities to the ones of CPs with one chemical shift range for protons on nonhalogenated carbons and one for protons with one halogen on the same carbon.展开更多
Halogenated natural products(HNPs)are considered to be emerging contaminants whose environmental distribution and fate are only incompletely known.Therefore,several persistent and bioaccumulative HNP groups,together w...Halogenated natural products(HNPs)are considered to be emerging contaminants whose environmental distribution and fate are only incompletely known.Therefore,several persistent and bioaccumulative HNP groups,together with manmade polychlorinated biphenyls(PCBs)and polybrominated diphenyl ethers(PBDEs),were quantified in the blubber of nine sperm whales(Physeter macrocephalus)stranded on the coast of the Mediterranean Sea in Italy.The naturally occurring polybrominated hexahydroxanthene derivatives(PBHDs;sum of TetraBHD and TriBHD)were the most prominent substance class with up to 77,000 ng/g blubber.The mean PBHD content(35,800 ng/g blubber)even exceeded the one of PCBs(28,400 ng/g blubber),although the region is known to be highly contaminated with manmade contaminants.Based on mean values,Q1∼PBDEs>MeO-BDEs∼2,2′-diMeO-BB 80 and several other HNPs followed with decreasing amounts.All blubber samples contained an abundant compound whose molecular formula(C_(16)H_(19)Br_(3)O_(2))was verified using high-resolution mass spectrometry.The only plausible matching isomer was(2S,4′S,9R,9′S)-2,7-dibromo-4′-bromomethyl-1,1-dimethyl-2,3,4,4′,9,9′-9,9′-hexahydro-1H-xanthen-9-ol(OH-TriBHD),a hydroxylated secondary metabolite previously detected together with TriBHD and TetraBHD in a sponge known to be a natural producer of PBHDs.The estimated mean amount of the presumed OH-TriBHD was 3000 ng/g blubber,which is unexpectedly high for hydroxylated compounds in the lipids of marine mammals.展开更多
Lipid biomarkers in AD2 penguin droppings-amend soil core from the Ardley Island,Western Antarctic,were dated using 210Pb.Changes in the fatty acid ratios of nC18:2/nC18:0 from the penguin droppings reflect climate ch...Lipid biomarkers in AD2 penguin droppings-amend soil core from the Ardley Island,Western Antarctic,were dated using 210Pb.Changes in the fatty acid ratios of nC18:2/nC18:0 from the penguin droppings reflect climate changes coincident with ENNO events during 1931-2006.The occurrence of the minimum values in the depth of 2-3 and 6-7 cm are consistent with the end of ENSO in 1958 and 1983,respectively,reflecting a lag of the biomarker records in AD2 penguin droppings-amend soil in climatic signatures.This study also reveals that the changes in the relative concentration of n-alkanes nC23,the ratios of nC23/nC17 and nC21 /nC22+,and carbon preferential index(CPI) values collectively indicate the variations of soil microor-ganism and lower plant,which are closely related to climate changes.The ratios of bacterial fatty acids iC15:0/aC15:0 reflect the increasing significance of microorganism activities during the two periods that occurred at the end years of ENSO.Decrease in CPIA value and increase in nC21 /nC22+ indicate that low molecular weight fatty acids are derived from microorganism;and their insignificant correlation with Pr/Ph suggests microorganisms play an important role in the relatively simply ecosystem in the Antarctic and are closely linked to climatic conditions.In addition,the observed penguin community indicates the popula-tion of penguin can largely reflect the impacts of global climate changes on the ecosystem.展开更多
The historical data of phytoplankton and chlorophyll a(Chl a)(1990–2002)obtained during the Chinese National Antarctic Research Expedition(CHINARE)in the Prydz Bay have been integrated.The results showed that the tem...The historical data of phytoplankton and chlorophyll a(Chl a)(1990–2002)obtained during the Chinese National Antarctic Research Expedition(CHINARE)in the Prydz Bay have been integrated.The results showed that the temperature,salinity,nutrients,and oxygen of seawater changed when El Nino/La Nina occurred.The variation of biological communities reflected the response of ecosystem to environmental changes.During El Ni?o period,Chl a concentration and phytoplankton community structure changed significantly,and the relative proportion of diatoms increased while dinoflagellates decreased.During La Ni?a period,the proportion of diatoms decreased,but the golden-brown algae and blue-green algae increased significantly.The variation of phytoplankton population directly affected the biodiversity of the bay,which were also quite sensitive to the marine environment changes.Meanwhile,the satellite remote sensing data of 2002–2011(December–March)have been used to study the temporal connection change of Chl a and phytoplankton in the Prydz Bay.We found that there were significant differences in the monthly variation characteristics of satellite remote sensing Chl a and sea surface temperature(SST),which had some links with sea ice melting and El Ni?o/La Ni?a events.We found that the start time of bloom advanced,lagged or synchronized with the changes of the SST,and we also found the occurrence time of phytoplankton bloom corresponded with the sea ice melting inner bay.To some extent,this study will help us understand the relationships between ENSO events and the phytoplankton bloom in the Southern Ocean.展开更多
文摘Brominated-chlorinated paraffins(Br-CPs)are a comparably new compound class that features both Cl and Br atoms on one or several alkane backbones.Due to legal restrictions in the use of conventional chlorinated paraffins(CPs),Br-CPs have the potential to become emerging contaminants.Currently,their determination is hampered by the lack of suitable reference standards.Here,we present a simple synthesis procedure with single chain alkanes that leads to Br-CPs with∼4–8 chlorine and 1 to 4 bromine substituents according to gas chromatography with electron capture negative ion mass spectrometry(GC/ECNI-MS).The single-chain Br-CP mixtures were obtained by the shared chlorination and bromination of eight single-chain alkanes(C10 to C17)at two reaction times,respectively.The carbon content of the 16 single-chain Br-CP products,determined by elemental analysis(EA),ranged from 30.8 to 43.8%.The typical hump peak known from CPs was detected with GC with flame ionization detection(GC/FID),electron capture detection(GC/ECD)and GC/ECNI-MS.The complexity indicated that low-resolution mass spectrometry is not sufficient for an adequate analysis of Br-CPs.A mathematical formula was developed which allows to calculate all possible combinations of Br and Cl that are in line with the carbon content.The proton magnetic resonance spectroscopy(1H NMR)spectra showed similarities to the ones of CPs with one chemical shift range for protons on nonhalogenated carbons and one for protons with one halogen on the same carbon.
文摘Halogenated natural products(HNPs)are considered to be emerging contaminants whose environmental distribution and fate are only incompletely known.Therefore,several persistent and bioaccumulative HNP groups,together with manmade polychlorinated biphenyls(PCBs)and polybrominated diphenyl ethers(PBDEs),were quantified in the blubber of nine sperm whales(Physeter macrocephalus)stranded on the coast of the Mediterranean Sea in Italy.The naturally occurring polybrominated hexahydroxanthene derivatives(PBHDs;sum of TetraBHD and TriBHD)were the most prominent substance class with up to 77,000 ng/g blubber.The mean PBHD content(35,800 ng/g blubber)even exceeded the one of PCBs(28,400 ng/g blubber),although the region is known to be highly contaminated with manmade contaminants.Based on mean values,Q1∼PBDEs>MeO-BDEs∼2,2′-diMeO-BB 80 and several other HNPs followed with decreasing amounts.All blubber samples contained an abundant compound whose molecular formula(C_(16)H_(19)Br_(3)O_(2))was verified using high-resolution mass spectrometry.The only plausible matching isomer was(2S,4′S,9R,9′S)-2,7-dibromo-4′-bromomethyl-1,1-dimethyl-2,3,4,4′,9,9′-9,9′-hexahydro-1H-xanthen-9-ol(OH-TriBHD),a hydroxylated secondary metabolite previously detected together with TriBHD and TetraBHD in a sponge known to be a natural producer of PBHDs.The estimated mean amount of the presumed OH-TriBHD was 3000 ng/g blubber,which is unexpectedly high for hydroxylated compounds in the lipids of marine mammals.
基金supported by National Natural Science Foundation of Chi-na (Grant Nos.40876104 and 41006118)
文摘Lipid biomarkers in AD2 penguin droppings-amend soil core from the Ardley Island,Western Antarctic,were dated using 210Pb.Changes in the fatty acid ratios of nC18:2/nC18:0 from the penguin droppings reflect climate changes coincident with ENNO events during 1931-2006.The occurrence of the minimum values in the depth of 2-3 and 6-7 cm are consistent with the end of ENSO in 1958 and 1983,respectively,reflecting a lag of the biomarker records in AD2 penguin droppings-amend soil in climatic signatures.This study also reveals that the changes in the relative concentration of n-alkanes nC23,the ratios of nC23/nC17 and nC21 /nC22+,and carbon preferential index(CPI) values collectively indicate the variations of soil microor-ganism and lower plant,which are closely related to climate changes.The ratios of bacterial fatty acids iC15:0/aC15:0 reflect the increasing significance of microorganism activities during the two periods that occurred at the end years of ENSO.Decrease in CPIA value and increase in nC21 /nC22+ indicate that low molecular weight fatty acids are derived from microorganism;and their insignificant correlation with Pr/Ph suggests microorganisms play an important role in the relatively simply ecosystem in the Antarctic and are closely linked to climatic conditions.In addition,the observed penguin community indicates the popula-tion of penguin can largely reflect the impacts of global climate changes on the ecosystem.
基金supported by the National Natural Science Foundation of China(Grant Nos.40876104,41076134,41306202,and 41376193)the Scientific Research Fund of the Second Institute,SOA(Grant Nos.JT1208,JG1217 and JG1218)
文摘The historical data of phytoplankton and chlorophyll a(Chl a)(1990–2002)obtained during the Chinese National Antarctic Research Expedition(CHINARE)in the Prydz Bay have been integrated.The results showed that the temperature,salinity,nutrients,and oxygen of seawater changed when El Nino/La Nina occurred.The variation of biological communities reflected the response of ecosystem to environmental changes.During El Ni?o period,Chl a concentration and phytoplankton community structure changed significantly,and the relative proportion of diatoms increased while dinoflagellates decreased.During La Ni?a period,the proportion of diatoms decreased,but the golden-brown algae and blue-green algae increased significantly.The variation of phytoplankton population directly affected the biodiversity of the bay,which were also quite sensitive to the marine environment changes.Meanwhile,the satellite remote sensing data of 2002–2011(December–March)have been used to study the temporal connection change of Chl a and phytoplankton in the Prydz Bay.We found that there were significant differences in the monthly variation characteristics of satellite remote sensing Chl a and sea surface temperature(SST),which had some links with sea ice melting and El Ni?o/La Ni?a events.We found that the start time of bloom advanced,lagged or synchronized with the changes of the SST,and we also found the occurrence time of phytoplankton bloom corresponded with the sea ice melting inner bay.To some extent,this study will help us understand the relationships between ENSO events and the phytoplankton bloom in the Southern Ocean.
