Chlordane Compounds Research Articles

Influencing Factors and Ecological Risks of Organochlorine Pesticide Adsorption in Surface Sediments of Qingshui River

ABSTRACT Taking the first-level tributary of Ningxia section of the Yellow River (Qingshui River) as the study area, surface sediment samples were collected during the seasons in 2018. The distribution characteristics, pollution levels, possible sources, influencing factors, and ecological risks of organochloride pesticides (OCPs) in the surface sediments were studied. The detected mean amounts were n.d. ~10.640 (1.474) ng·g−1, and the detection rate was 80.95%. The content (mean values) of Hexachlorocyclohexanes (HCHs), Endosulfan, Chlordane, and Dichlorodiphenyltrichloroethane (DDT) with higher detection amounts and detection rates were n.d. ~0.949 (0.153), n.d. ~1.973 (0.331), n.d. ~0.271 (0.052), and n.d. ~10.583 (0.819) ng·g−1, respectively. The total OCP amounts were detected in Changshantou and Liwang research sections, which have surrounding farmlands and low water flow. The total organic carbon plays a vital role in the residue and distribution of β-HCH and Dieldrin. In a high-salinity environment, the lower-layer sediments had higher adsorption efficiencies for DDT and γ-HCH and the HCH content decreased with the increase in pH. The total nitrogen and phosphorus in sediments were among the controlling factors affecting the distribution of Endosulfan II and p,p’-DDT, respectively, but their effects on Dieldrin only appeared in the spring flood season. Further, a functional model was established with respect to the adsorption amount of various OCPs and the influencing factors. The component analysis results showed that OCPs primarily originated from historical residues; however, only small amounts of Lindane, Dicofol, Endosulfan, and Chlordane compounds have been observed recently in the local environment. Using the low-effect interval and median method for potential ecological risk assessment, Endosulfan was noted to have potential ecological risks, mainly distributed in the middle and lower reaches of the river. The reasons for the potential harm require attention and further research.

Persistent organic pollutants in human milk of Belgian mothers: levels, time trend and exposure assessment for nursing infants

Human milk samples (n = 206) collected in 2014 from Belgian primiparous mothers were analyzed for seven groups of persistent organic pollutants (POPs): dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), polybrominated diphenyl ethers (PBDEs), pentachlorobenzene (PeCB), and hexabromobiphenyl (BB-153). Pooled samples for the analysis of hexachlorobutadiene, heptachlor, chlordecone, dieldrin, and hexabromocyclododecane (HBCD) were prepared. DDTs [median: 41 ng/g lipid weight (lw)], HCB (5.5 ng/g lw), and HCHs (2.4 ng/g lw) were the predominant compounds in all samples. Median levels of PBDEs (0.91 ng/g lw) in Belgian human breast milk samples were lower compared to other European countries. The major PBDE congeners were BDE-47 and BDE-153, and total PBDE levels were low (0.30-4.25 ng/g lw). α-HBCD was the only HBCD stereoisomer found in the pooled milk samples (2.5 ng/g lw). All targeted POPs were determined in a national pooled sample but were lower than levels of most POPs [organochlorine pesticides (OCPs), PBDEs, and polychlorinated biphenyls (PCBs)] observed in 2006. The daily dietary intake of POPs via human milk was estimated for nursing infants of 1 month [intake of 260 mL milk/kg body weight (bw)] and compared with either health-based guidance values (HBGV) or the reference point (margin of exposure, MOE). The exposure assessment in a worst-case scenario revealed no concern for most POPs. However, the infants were exposed to levels of 60 pg total WHO2005-TEQ/kg bw/week, indicating a possible risk during their life. Based on the MOE approach, 95th percentile of concentration can result in a health concern for congeners BDE-99 and BDE-153.

Organochlorine pesticides and their markers of exposure in serum and urine of children from a nodding syndrome hotspot in northern Uganda, east Africa

Nodding syndrome (NS) is a neurologic disorder of unknown etiology characterized by vertical head nodding that has affected children aged 5–18 years in East Africa. Previous studies have examined relationships with biological agents (e.g., nematodes, measles, and fungi), but there is limited data on the possible contributions of neurotoxic environmental chemicals frequently used as pesticides/insecticides to the development and progression of this disorder. We examined the levels of persistent organochlorine pesticides (OCPs) in children (5–18 years old) from Kitgum District, Northern Uganda. These children previously lived in internally displaced people's (IDP) camps, where they were exposed to various health risks, including contaminated food and water. Exposure to OCPs through contaminated food and water is postulated here as a potential contributor to NS etiology. We analyzed serum (n = 75) and urine (n = 150) samples from children diagnosed with NS, and from seizure-free household controls (HC), and community controls (CC). Samples were extracted using solid-phase extraction (SPE) and extracts were analyzed for OCPs using gas chromatography with a triple quadrupole mass spectrometry (GC-MS/MS). Mean levels of total (∑) ∑OCPs in serum samples from NS, HC and CC subjects were 23.3 ± 2.82, 21.1 ± 3.40 and 20.9 ± 4.24 ng/mL, respectively, while in urine samples were 1.86 ± 1.03, 2.83 ± 1.42, and 2.14 ± 0.94 ng/mL, respectively. Correlation and linear regression analysis indicated that potential markers for ∑hexachlorocyclohexanes (HCHs), ∑chlordane compounds (CHLs), ∑endosulfan and ∑dichlorodiphenyltrichloroethanes (DDTs) were γ-HCH, heptachlor-exo-epoxide, endosulfan-α and p,pʹ-DDD in NS cases while in controls were α –HCH, heptachlor, endosulfan-α and p,pʹ-DDE, respectively. Since, in some instances, higher OCP levels were found in controls vs. NS cases, we conclude that exposure to organochlorine pesticides is unlikely to be associated with the etiology of NS.

Impacts of a warming climate on concentrations of organochlorines in a fasting high arctic marine bird: Direct vs. indirect effects?

The present study examined how climate changes may impact the concentrations of lipophilic organochlorines (OCs) in the blood of fasting High Arctic common eiders (Somateria mollissima) during incubation. Polychlorinated biphenyls (PCBs), 1-dichloro-2,2-bis (p-chlorophenyl) ethylene (p,p′-DDE), hexachlorobenzene (HCB) and four chlordane compounds (oxychlordane, trans-chlordane and trans- and cis-nonachlor) were measured in females at chick hatching (n = 223) over 11 years (2007–2017). Firstly, median HCB and p,p′-DDE concentrations increased ~75 % over the study period, whereas median chlordane concentrations doubled (except for oxychlordane). PCB concentrations, in contrast, remained stable over the study period. Secondly, both body mass and clutch size were negatively associated with OC levels, suggesting that females with high lipid metabolism redistributed more OCs from adipose tissue, and that egg production is an important elimination route for OCs. Thirdly, the direct climate effects were assessed using the mean effective temperature (ET: air temperature and wind speed) during incubation, and we hypothesized that a low ET would increase redistribution of OCs. Contrary to expectation, the ET was positively correlated to most OCs, suggesting that a warmer climate may lead to higher OCs levels, and that the impact of ET may not be direct. Finally, potential indirect impacts were examined using the Arctic Oscillation (AO) in the three preceding winters (AOwinter 1–3) as a proxy for potential long-range transport of OCs, and for local spring climate conditions. In addition, we used chlorophyll a (Chla) as a measure of spring primary production. There were negative associations between AOwinter 1 and HCB, trans-chlordane and trans-nonachlor, whereas oxychlordane and cis-chlordane were negatively associated with Chla. This suggests that potential indirect climate effects on eiders were manifested through the food chain and not through increased long-range transport, although these relationships were relatively weak.

Temporal trends of persistent organic pollutant contamination in Franciscana dolphins from the Southwestern Atlantic

Persistent organic pollutants (POPs) were analyzed in 136 blubber samples of Franciscana dolphins from Brazil (Pontoporia blainvillei), which is the most threatened dolphin in the Southwestern Atlantic. The dolphins were caught by the fishery fleet and collected from 2000 to 2018 in three regions of São Paulo state: northern São Paulo (SPN), central São Paulo (SPC), and southern São Paulo (SPS). The POPs analyzed in this study were polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDTs), Mirex, hexachlorobenzene (HCB), chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs), and polybrominated diphenyl ethers (PBDEs). The concentrations ranged from 36 to 7200 ng g−1 lipid weight (lw) and 113–42200 ng g−1 lw for predominant compounds DDTs and PCBs, respectively. Similar profiles of PCB congeners were observed with a predominance of hexachlorinated compounds, representing approximately 50% of the total PCB amount; the highest PCB concentrations were observed from Baixada Santista (SPC) proximate to a highly urbanized and industrial coastal area. Significant differences were observed between the sexes and maturity of dolphins, mainly for PCBs, DDTs, and Mirex. In general, POPs other than HCB in Franciscana dolphins showed downward temporal trends, matching the regulatory periods for restricting and/or banning these compounds. Although POP concentrations are declining, PCB levels remain high in small dolphins, suggesting adverse health effects on Franciscanas. As organic contaminants are one of the numerous threats Franciscanas have been vulnerable to along the Brazilian coast, we recommend monitoring POPs levels every five years to check for declining (or stabilizing) trends.

Flavonoids and organochlorines in honey from the Ryukyu Islands, Japan

PurposeThe purpose of this study is to analyze the flavonoid composition and organochlorine compounds (OCs) in honey samples from different floral sources on the Ryukyu Islands of Japan, and to determine their nutritional characteristics and the risk of intaking hazardous pollutants.Design/methodology/approachHoney samples were collected from various regions of the Ryukyu Islands. Thirty-one samples were analyzed for six flavonoid compounds by high-performance liquid chromatography, and OCs from 14 samples were analyzed by gas chromatography. The differences in flavonoid composition among the samples from different floral sources were determined.FindingsHoney from Bidens pilosa L. var. radiata Sch. Bip. contained high concentrations of luteolin and apigenin. One sample with polychlorinated biphenyls and two with chlordane compounds were detected in one region; however, their concentrations were lower than those for food regulations.Originality/valueNovel chemical characteristics in Ryukyu honey, including high amounts of luteolin and apigenin from B. pilosa, were discovered, whereas low OC contamination was observed.

The association between environmental exposures to chlordanes, adiposity and diabetes-related features: a systematic review and meta-analysis

Chlordane compounds (CHLs) are components of technical chlordane listed in the Stockholm convention on persistent organic pollutants identified as endocrine disrupting chemicals (EDCs) and may interfere with hormone biosynthesis, metabolism or action resulting in an unbalanced hormonal function. There is increasing scientific evidence showing EDCs as risk factors in the pathogenesis and development of obesity and obesity-related metabolic syndromes such as type 2 diabetes, but there is no systematized information on the effect of CHLs in humans. Our aim is to identify the epidemiological data on the association between CHLs with adiposity and diabetes using a systematic approach to identify the available data and summarizing the results through meta-analysis. We searched PubMed and Web of Science from inception up to 15 February 2021, to retrieve original data on the association between chlordanes, and adiposity or diabetes. For adiposity, regression coefficients and Pearson or Spearman correlation coefficients were extracted and converted into standardized regression coefficients. Data were combined using fixed effects meta-analyses to compute summary regression coefficients and corresponding 95% confidence intervals (95% CI). For the association between chlordanes and diabetes, Odds ratios (ORs) were extracted and the DerSimonian and Laird method was used to compute summary estimates and respective 95% CI. For both, adjusted estimates were preferred, whenever available. Among 31 eligible studies, mostly using a cross-sectional approach, the meta-analysis for adiposity was possible only for oxychlordane and transchlordane, none of them were significantly associated with adiposity [(β = 0.04, 95% CI 0.00; 0.07, I2 = 89.7%)] and (β = 0.02, 95% CI − 0.01; 0.06), respectively. For diabetes, the estimates were positive for all compounds but statistically significant for oxychlordane [OR = 1.96 (95% CI 1.19; 3.23)]; for trans-nonachlor [OR = 2.43 (95% CI 1.64; 3.62)] and for heptachlor epoxide [OR = 1.88 (95% CI 1.42; 2.49)]. Our results support that among adults, the odds of having diabetes significantly increase with increasing levels of chlordanes. The data did not allow to reach a clear conclusion regarding the association with adiposity.

Contamination of habu (Protobothrops flavoviridis) in Okinawa, Japan by persistent organochlorine chemicals

Persistent organochlorine chemicals (OCs), including chlordane compounds (CHLs), DDTs, PCBs, and chlorinated dioxins and related compounds (DRCs), were examined in the adipose tissue and liver from 33 specimens of habu (Protobothrops flavoviridis), a species of venomous pit viper endemic to the Japanese Southwest Islands. The median concentrations of CHLs, DDTs, and PCBs in adipose tissue of 22 habus collected from an urban area were 4400 ng g-1 lipid weight (lw), 610 ng g-1 lw, and 1600 ng g-1 lw, respectively. Their DDT and PCB concentrations were higher in comparison with the specimens from a rural area. Liver of 10 specimens from the urban area were subjected to DRCs analysis, and PCDDs, PCDFs, and DL-PCBs were detected with median values of 1300, 350, and 150,000 pg g-1 lw, respectively. Among PCDD/F congeners, octa-CDD was detected at the highest concentrations in seven liver samples, but considerable concentrations of penta- and hexa-CDD/Fs were found in two samples. Relatively higher concentrations of PCB, DDTs, and PCDD/Fs were found in habus collected within 1 km of the boundary of military facilities, suggesting that OCs from some unknown sources of these OCs inside and/or around some of the facilities accumulated in habus.

Air-water exchange and distribution pattern of organochlorine pesticides in the atmosphere and surface water of the open Pacific ocean

Surface seawater and lower atmosphere gas samples were collected simultaneously between 18°N and 40°S in the open Pacific Ocean in 2006–2007. Samples were analyzed for organochlorine pesticides (OCPs) to assess their distribution patterns, the role of ocean in the long-range transport (LRT), and the air-water exchange directions in the open Pacific Ocean. Such open ocean studies can yield useful information such as establishing temporal and spatial trends and assessing primary vs secondary emissions of legacy OCPs. Target compounds included hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and its derivatives, and chlordane compounds. Concentrations for α-HCH, γ-HCH, trans-chlordane (TC), and cis-chlordane (CC) were higher in the Northern Hemisphere (NH) than the Southern Hemisphere (SH) in both gaseous and dissolved phases, while the distribution patterns of DDTs and heptachlor exo-epoxide (HEPX) showed a reversed pattern. In the N Pacific, concentrations of α-HCH and γ-HCH in the present work were lower by 63 and 16 times than those observed in 1989–1990. The distribution patterns of DDT suggested there was usage in the SH around 2006. Calculated fugacity ratios suggested that γ-HCH was volatilizing from surface water to the atmosphere, and the air-water exchange fluxes were 0.3–11.1 ng m−2 day−1. This is the first field study that reported the open Pacific Ocean has become the secondary source for γ-HCH and implied that ocean could affect LRT of OCPs by supplying these compounds via air-sea exchange.

Coastal biomonitoring survey on persistent organic pollutants using oysters (Saccostrea mordax) from Okinawa, Japan: Geographical distribution and polystyrene foam as a potential source of hexabromocyclododecanes

The present study determined contamination levels of POPs, such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs), in oysters (Saccostrea mordax) collected throughout the seacoast of Okinawa, Japan and their geographic distribution. PCBs, DDTs, CHLs, PBDEs and HBCDs were detected in almost all the oyster samples analyzed and higher concentrations of PCBs, DDTs and CHLs were found in oysters from southwestern populated areas. On the other hand, HBCDs in oysters showed similar levels throughout Okinawa and the highest concentration in a northern rural site with less human and industrial activities, although oyster concentrations of PBDEs were relatively lower. When POPs in expanded polystyrene (EPS) buoys and polystyrene foam debris floated and drifted on coastal seawater were analyzed, extremely high concentrations of HBCDs were detected in some of these EPS buoys and polystyrene foam debris but other POPs were below the limit of detection in all the samples. To evaluate the specific exposure route of HBCDs for oysters, we further analyzed HBCD diastereomers, and PCB congeners by way of comparison, in seawater and sediment samples collected at an urban site and a rural site and estimated their biota (oyster)-sediment accumulation factors (BSAF) and bioaccumulation factors (BAF). Interestingly, the highest log BAF values were found for α-HBCD despite its lower log Kow than those of γ-HBCD and PCB congeners, although log BSAF values for HBCDs were lower than those for PCBs. Considering that α-HBCD was detected in a few polystyrene foam samples as the predominant diastereomer, oysters inhabiting the coastal region of Okinawa might be frequently exposed to micronized polystyrene foam particles containing HBCDs.

Interspecies comparison of the residue levels and profiles of persistent organic pollutants in terrestrial top predators

Serum samples from three species of living terrestrial top predators were analysed for six groups of persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB) and polybrominated diphenyl ethers (PBDEs). The study included three carnivore species: lion (Panthera leo), hyena (Hyena brunnea) and cheetah (Acinonyx jubatus). All samples were collected from healthy living animals between 2004 and 2005. Most of the samples (wild lions (n = 50) and hyenas (n = 11)) were collected from various locations within the Kruger National Park and Addo National Park (South Africa), while captive lions (n = 6) and cheetahs (n = 3) were collected from the Antwerp Zoo (Belgium). In general, relatively low levels of POPs were found in the studied species, varying widely within species and locations. Median concentrations of POPs were higher in captive lions (PCBs: 505 pg/mL; DDTs: 270 pg/mL; HCHs: 72 pg/mL; HCB: 34 pg/mL; CHLs: 24 pg/mL; PBDEs: 8 pg/mL) compared to wild lions (DDTs: 274 pg/mL; HCHs: 44 pg/mL; CHLs: 7.9 pg/mL; PCBs: 2.1 pg/mL; HCB: < LOQ; PBDEs: < LOQ). In the wild animals, POPs accumulated in the following order: DDTs > HCHs > CHLs > HCB > PCBs > PBDEs, while in the captive animals, the order was: PCBs > DDTs > CHLs > HCHs > HCB > PBDEs, suggesting differences in the diet of these animals. Furthermore, wild hyena contained significantly higher (p < 0.05) median levels of POPs compared to wild lions, possibly reflecting differences in metabolic capacity and/or feeding habits, together with an uneven distribution of POPs in the area where the animals lived. No previous data are available to compare for similar terrestrial top predators, such as lion, hyena and cheetah. To our knowledge, this is first study on POPs in these three species. The low POP levels found in this study were several orders of magnitude lower than those for other carnivore species, such as polar bears, grizzly bears, brown bears and wolves worldwide. The present study has revealed the need for expanding research and monitoring on occurrence, levels and disposition of POPs in the top predators of the terrestrial environment.

Polyurethane foam disk passive sampler derived air concentrations of persistent organic pollutants in an agricultural region with hot climate

Polyurethane foam (PUF) disks passive air samplers were deployed in an agricultural region with hot climate to determine atmospheric concentrations of 22 organochlorine pesticides (OCPs) and 15 polychlorinated biphenyls (PCBs). Sampling rates (2.39–15.9 m3.day−1) increased with rising ambient air temperatures. Total OCP and PCB concentrations were 0.884–97.0 pg.m−3 and nd-213 pg.m−3, respectively. The most prominent OCPs in the samples were hexachlorocyclohexane (HCH) isomers, chlordane compounds, dichlorodiphenyltrichloroethane (DDT) derivatives, and endosulfan isomers. The isomer ratios of DDT and Chlordane in the samples indicated older usage while endosulfan ratios showed recent input of technical endosulfan in the region. Total PCB levels were dominated by low chlorinated congeners. The contaminant levels in air samples were mainly lower or similar by comparison to other studies conducted at agricultural regions worldwide. Although the production and use of these chemicals have been banned, results of this study show that some of the chemicals could still be found in agricultural areas. Presence of these chemicals in environmental samples may be result of the degradation of formerly used chemicals, atmospheric transport or illegal use of banned chemicals.

Occurrence of organochlorine compounds in fish from freshwater environments of the central Andes, Argentina.

The Central Andes region is considered an area of high environmental relevance in South America and it is rich in glaciers, which are the main fresh water sources and reservoirs of the region. The presence of organochlorine compounds (OCs) is an environmental threat due to their persistence and adverse effects on wildlife and humans. The levels of OCs, such as chlordane compounds (CHLs), dichlorodiphenyltrichloroethane and metabolites (DDTs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), and polychlorinated biphenyls (PCBs), were determined in muscle and liver tissues of fish and in sediments collected from different sites of the central Andes: the Mendoza River and the Yaucha River (rainbow trout: Oncorhynchus mykiss) and Carrizal Dam (silverside: Odontesthes bonariensis). Regardless of studied site and fish tissue, the general OC trend was: DDTs > PCBs > HCHs > CHLs > HCB. The results showed clear geographic distribution patterns for DDTs. Among the sampling sites, silverside fish showed the highest average load of DDTs (614 and 867 ng g-1 lw in muscle and liver tissues, respectively). Based on the biota-sediment bioaccumulation factor (BSAF), both rainbow trout and silverside fish showed comparable capability to accumulate p,p'-DDT in their tissues. Intraspecific correlational analysis showed that CB-138 in muscle and p,p'-DDT in liver were clearly correlated with the lipid content in silverside specimens, which highlights the relevance of taking into account the fat content and the type of target tissues.

Dynamics of persistent organic pollutants in obese adolescents during weight loss

We have investigated the dynamics of various persistent organic pollutants (POPs) in the serum of 94 obese adolescents (34 boys and 60 girls: age range 11–19years) before (0M) and after 5months (5M) of undergoing weight loss treatment. Six groups of POPs, such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB) and polybrominated diphenyl ethers (PBDEs), were detected in all samples in the decreasing order of median levels: DDTs>PCBs>HCB>HCHs>CHLs>PBDEs. Levels and patterns of POPs between boys and girls at two time-points were similar. DDTs (0M/5M; median: 31/42ng/g lw) and PCBs (0M/5M; median: 17/28ng/g lw) were the major POPs. PCB 153 (0M/5M; 33/34% of the sum PCBs) was the most dominant PCB congener, followed by PCB 138 (0M/5M; 31/31%) and PCB 180 (0M/5M; 13/12%), respectively. The most important PBDE congeners were BDE 47 and 153, although total PBDE levels were low and ranged between 0.63 and 0.88ng/g lw. In general, levels of POPs in the obese adolescents were lower than previously reported in Belgian adolescents and adults. Due to weight loss, serum levels (except PBDEs) increased significantly thereafter combined with a body weight decrease (from 4 to 42kg). Serum concentrations increased by 1–3.5% per kilogram weight loss and 1–2.5% per BMI z-score loss for most POPs. To our knowledge, this is the first report on the dynamics of POPs in obese adolescents during weight loss. Lipid-soluble contaminants were released from adipose tissue into the blood leading to redistribution into the body. Whether the increase in the internal exposure to POPs may adversely influence health remains to be determined.

Linking pollutant exposure of humpback whales breeding in the Indian Ocean to their feeding habits and feeding areas off Antarctica

Humpback whales, Megaptera novaeangliae, breeding off la Reunion Island (Indian Ocean) undergo large-scale seasonal migrations between summer feeding grounds near Antarctica and their reproductive winter grounds in the Indian Ocean. The main scope of the current study was to investigate chemical exposure of humpback whales breeding in the Indian Ocean by providing the first published data on this breeding stock concerning persistent organic pollutants (POPs), namely polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), DDT and its metabolites (DDTs), chlordane compounds (CHLs), polybrominated diphenyl ethers (PBDEs), and methoxylated PBDEs (MeO-PBDEs). Analyses of stable isotopes δ13C and δ15N in skin resulted in further insight in their feeding ecology, which was in agreement with a diet focused mainly on low trophic level prey species, such as krill from Antarctica. POPs were measured in all humpback whales in the order of HCB > DDTs > CHLs > HCHs > PCBs > PBDEs > MeO-BDEs. HCB (median: 24 ng g−1 lw) and DDTs (median: 7.7 ng g−1 lw) were the predominant compounds in all whale biopsies. Among DDT compounds, p,p′-DDE was the major organohalogenated pollutant, reflecting its long-term accumulation in humpback whales. Significantly lower concentrations of HCB and DDTs were found in females than in males (p < 0.001). Other compounds were similar between the two genders (p > 0.05). Differences in the HCB and DDTs suggested gender-specific transfer of some compounds to the offspring. POP concentrations were lower than previously reported results for humpback whales sampled near the Antarctic Peninsula, suggesting potential influence of their nutritional status and may indicate different exposures of the whales according to their feeding zones. Further investigations are required to assess exposure of southern humpback whales throughout their feeding zones.

Brominated flame retardants and organochlorine compounds in duplicate diet samples from a Portuguese academic community

Concentrations of persistent organic pollutants (POPs), including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), chlordane compounds (CHLs) and dichlorodiphenyltrichloroethane and its metabolites (DDTs), were measured in duplicate diet samples from 21 volunteers at a Portuguese academic community (University of Aveiro). Overall, the levels of the target compounds were low, with detection frequencies varying widely depending on the compounds and with brominated flame retardants (BFRs) registering the lowest detection frequencies. Among PCB congeners, nondioxin-like PCBs were predominant and detected in the majority of the samples. Organochlorine pesticides were also detected in the majority of the samples, with 100% detection for DDTs and HCHs.Estimated daily intakes (EDIs) were calculated using lower and upper bound estimations, and in both cases values were far below the currently established tolerable daily intakes for PCBs and OCs and the reference doses for PBDEs and HBCDDs.

Levels and profiles of brominated and chlorinated contaminants in human breast milk from Thessaloniki, Greece

Human breast milk samples (n=87) collected between July 2004 and July 2005 from primipara and multipara mothers from Thessaloniki, Greece were analysed for six groups of persistent organic pollutants (POPs): polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs) and hexachlorobenzene (HCB). DDTs [median: 410ng/g lipid weight (lw)], PCBs (median: 90ng/g lw) and HCHs (median: 40ng/g lw) were the predominantly identified compounds in all the breast milk samples. Levels of PBDEs (median: 1.5ng/g lw) in human breast milk samples from Thessaloniki, Greece were lower compared to other countries. Maternal age had a positive correlation with most compounds, but not with PBDEs. Women with a higher occupational exposure to PBDEs (i.e., working in office environments) had higher PBDE concentrations than all others and showed strong correlations, especially for BDE 47 and BDE 153. None of the analysed compounds showed any correlation with parity. Based on these levels, the daily intake of each group of POPs via human milk was calculated and compared with the tolerable daily intakes (TDI) or the reference doses (RfD). For the majority of samples (85 out of 87) a higher daily intake of PCBs than the TDI was calculated, while 11 out of 87 samples had a higher HCB intake than the TDI. The TDI and the RfD were not exceeded for DDTs and PBDEs, respectively. This is the first report of brominated flame retardants in human breast milk from Greece.

20 Years of Air–Water Gas Exchange Observations for Pesticides in the Western Arctic Ocean

The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air-water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water-air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air-surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals.

Persistent Organochlorine Pesticide Exposure Related to a Formerly Used Defense Site on St. Lawrence Island, Alaska: Data from Sentinel Fish and Human Sera

St. Lawrence Island, Alaska, is the largest island in the Bering Sea, located 60 km from Siberia. The island is home to approximately 1600 St. Lawrence Island Yupik residents who live a subsistence way of life. Two formerly used defense sites (FUDS) exist on the island, one of which, Northeast Cape, has been the subject of a $123 million cleanup effort. Environmental monitoring demonstrates localized soil and watershed contamination with polychlorinated biphenyls (PCB), organochlorine (OC) pesticides, mercury, and arsenic. This study examined whether the Northeast Cape FUDS is a source of exposure to OC pesticides. In total, 71 serum samples were collected during site remediation from volunteers who represented three geographic regions of the island. In addition, ninespine stickleback (Pungitius pungitius) and Alaska blackfish (Dallia pectoralis) were collected from Northeast Cape after remediation to assess continuing presence of OC pesticides. Chlordane compounds, DDT compounds, mirex, and hexachlorobenzene (HCB) were the most prevalent and present at the highest concentrations in both fish tissues and human serum samples. After controlling for age and gender, activities near the Northeast Cape FUDS were associated with an increase in serum HCB as compared to residents of the farthest village from the site. Positive but nonsignificant relationships for sum-chlordane and sum-DDT were also found. Organochlorine concentrations in fish samples did not show clear geographic trends, but appear elevated compared to other sites in Alaska. Taken together, data suggest that contamination of the local environment at the Northeast Cape FUDS may increase exposure to select persistent OC pesticides.

Air-Seawater Exchange of Organochlorine Pesticides along the Sediment Plume of a Large Contaminated River.

Gaseous exchange fluxes of organochlorine pesticides (OCPs) across the air-water interface of the coastal East China Sea were determined in order to assess whether the contaminated plume of the Yangtze River could be an important regional source of OCPs to the atmosphere. Hexachlorocyclohexanes (HCHs), chlordane compounds (CHLs), and dichlorodiphenyltrichloroethanes (DDTs) were the most frequently detected OCPs in air and water. Air-water exchange was mainly characterized by net volatilization for all measured OCPs. The net gaseous exchange flux ranged 10-240 ng/(m2·day) for γ-HCH, 60-370 ng/(m2·day) for trans-CHL, 97-410 ng/(m2·day) for cis-CHL, and ∼0 (e.g., equilibrium) to 490 ng/(m2·day) for p,p'-DDE. We found that the plume of the large contaminated river can serve as a significant regional secondary atmospheric source of legacy contaminants released in the catchment. In particular, the sediment plume represented the relevant source of DDT compounds (especially p,p'-DDE) sustaining net degassing when clean air masses from the open ocean reached the plume area. In contrast, a mass balance showed that, for HCHs, contaminated river discharge (water and sediment) plumes were capable of sustaining volatilization throughout the year. These results demonstrate the inconsistencies in the fate of HCHs and DDTs in this large estuarine system with declining primary sources.