The rise of glyphosate and new opportunities for biosentinel early‐warning studies

Glyphosate has become the most commonly used herbicide worldwide and is reputedly environmentally benign, nontoxic, and safe for use near wildlife and humans. However, studies indicate its toxicity is underestimated and its persistence in the environment is greater than once thought. Its actions as a neurotoxin and endocrine disruptor indicate its potential to act in similar ways to persistent organic pollutants such as the organochlorines dichlorodiphenyltrichloroethane (DDT) and dioxin. Exposure to glyphosate and glyphosate‐based herbicides for both wildlife and people is likely to be chronic and at sublethal levels, with multiple and ongoing exposure events occurring in urban and agricultural landscapes. Despite this, there has been little research on the impact of glyphosate on wildlife populations, and existing studies appear in the agricultural, toxicology, and water‐chemistry literature that may have limited visibility among wildlife biologists. These studies clearly demonstrate a link between chronic exposure and neurotoxicity, endocrine disruption, cell damage, and immune suppression. There is a strong case for the recognition of glyphosate as an emerging organic contaminant and substantial potential exists for collaborative research among ecologists, toxicologists, and chemists to quantify the impact of glyphosate on wildlife and to evaluate the role of biosentinel species in a preemptive move to mitigate downstream impacts on people. There is scope to develop a decision framework to aid the choice of species to biomonitor and analysis methods based on the target contaminant, spatial and temporal extent of contamination, and perceived risk. Birds in particular offer considerable potential in this role because they span agricultural and urban environments, coastal, inland, and wetland ecosystems where glyphosate residues are known to be present.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Contribution of sociodemographic characteristics, occupation, diet and lifestyle to DDT and DDE concentrations in serum and adipose tissue from a Bolivian cohort

The organochlorine pesticide p,p′-Dichlorodiphenyltrichloroethane (DDT) was widely used in the early 1960s-70s for vector control in tropical and subtropical areas of South America. Due to its persistence, DDT has a high potential to bioaccumulate in the food chain and living organisms and is a major public health concern, especially in South America.The main purpose of the present study was to investigate predictors of serum and adipose tissue concentrations of p,p′-DDT and its main metabolite, p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE), in an adult cohort (n = 112) from Santa Cruz de la Sierra, Bolivia, using multiple linear regression models. These models explained 29.3-47.8% of the variability in adipose tissue concentrations of p,p′-DDT and p,p′-DDE, respectively, and 32.9-47.0% of that in serum. Main exposure predictors included age, occupational class, residence, diet, smoking habit, and accumulated breastfeeding time.This is one of the few studies to explore predictors of human exposure to these chemicals using a multivariate approach in a South American population. Results show that predictors of human exposure to p,p′-DDT and p,p′-DDE in Santa Cruz de la Sierra may diverge from those found in other populations of the world, due to particular sociodemographic and lifestyle characteristics of this region.     

Optimization of the recovery of plastics for recycling by density media separation cyclones

Material recovery processes are presented as the optimum option for recycling plastic wastes as a means of recovering hydrocarbon resources. There exist a large variety of automated material recovery processes for recycling of such wastes but each with significant limitations. Of these, the separation based on differences in densities is advocated as the optimum process either for producing recycled products or preparing wastes for subsequent recovery processing.Density separation processes based on cyclone type density media separation (DMS) is presented as an important, potential method for increasing plastics recycling process capacities. It is demonstrated to have the capacity to separate a significantly larger range of particle sizes than those presently processed industrially. The mathematical relationship for the prediction of quality of typical LARCODEMS type density media separations by particle size and density as expressed by the Ecart Probable is presented.A proposed device configuration is presented for density media separation to optimize the recovery and purity of both density fractions produced. It is also suggested that to be economically viable, a large scale of operation is required for industrial plastics recycling operations recovering and producing a number of different plastics with a purity to be used as a substitute for virgin material.     

Das neue Chemikalienprogramm von UNEP Chemicals

Zusammenfassung  UNEP International Register of Potentially Toxic Chemicals (IRPTC) wurde von der ersten VN-Umweltkonferenz 1972 geschaffen. Sein Einfu? und Zusammenwirken in den 80ziger Jahren mit anderen internationalen Programmen der WHO, FAO, OECD und EG in der Chemikalienkontrolle wird beschrieben. Nach dem Erdgipfel von Rio 1992 werden im VN-Rahmen drei neue Gremien gebildet, die das Fachprogramm des Kapitels 19 der Agenda 21 (umweltfreundliches Chemikalienmanagement) umsetzen sollen: die United nations Commission of Sustainable Development, das Intergovernmental Forum on Chemical Safety und das Interorganization Programme for the Sound Management of Chemicals. Der Erdgipfel brachte auch für IRPTC eine Neuorientierung. Seit 1996 hat UNEP Chemicals, wie sich IRPTC nunmehr nennt, drei Aufgaben in sein Arbeitsprogramm aufgenommen, die beschrieben werden: das internationale übereinkommen zum Prior Informed Consent, das internationale übereinkommen zur Kontrolle der Persistent Organic Pollutants, und schlie?lich sein traditionelles Arbeitsgebiet des Informations-austausches über Stoffe wird weitergeführt.

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Die Aussagen dieses Beitrages sind die Meinung des Autors. Sie müssen nicht mit der Auffassung des Umweitbundesamtes oder von UNEP Chemicals übereinstimmen.     

Incidence of thyroid disease following exposure to polybrominated biphenyls and polychlorinated biphenyls, Michigan, 1974-2006

Thyroid hormones, which influence body metabolism and development, could be affected by persistent organic pollutants. We sought to examine the relationship between polybrominated biphenyls (PBBs) and polychlorinated biphenyls (PCBs) and thyroid disease. We employed incidence density sampling to perform a nested case control analysis of the Michigan Long-Term PBB Cohort. Cohort members (n = 3333) were exposed to PBBs through contaminated cattle feed in 1973-1974 and to PCBs through daily life. Those with detectable serum PBB and PCB concentrations at enrollment were categorized into tertiles of PBB and PCB exposure. Case-patients were cohort members answering “Yes” to “Has a healthcare provider ever told you that you had a thyroid problem?” during follow-up interviews; control-patients were cohort members answering “No”. We used odds ratios (OR) with 95% confidence intervals (CI) to compare odds of thyroid disease by PBB and PCB exposure and by various risk factors. Total cumulative thyroid disease incidence after 33 years was 13.9% among women and 2.6% among men. After adjusting for body mass index, we found no statistically significant differences in odds of any type of thyroid disease among women or men with elevated PBB or PCB exposure. Compared to control-patients, women with thyroid disease had increased odds of being overweight/obese (OR = 2.82, 95% CI: 1.94-4.11) and developing infertility (OR = 1.71, 95% CI: 1.08-2.69), diabetes (OR = 1.61, 95% CI: 1.04-2.51), or arthritis (OR = 1.71, 95% CI: 1.18-2.50) during follow-up. Additional research should explore potential associations between PBBs/PCBs and thyroid disease among children exposed in utero.     

Seasonal variation of organochlorine contaminants in bonito (Sarda sarda L. 1758) and anchovy (Engraulis encrasicolus L. 1758) in Black Sea region, Turkey

The concentrations of indicator polychlorinated biphenyls (PCBs) and organochlorine insecticides were determined in bonito (Sardasarda L. 1758) and anchovy (Engraulisencrasicolus L. 1758) from the Black Sea, Turkey. Concentrations of total indicator PCBs ranged between <1-17.0 in bonito, and <1-17.5 ng/g fresh weight in anchovy, and total of 1,1,1-trichloro-2,2-bis-chlorophenyl-ethane and its metabolites’ (DDTs) concentrations ranged between 13.4-26.3, and 2.96-19.0 ng/g fresh weight in bonito and anchovy respectively. PCB 52, p,p′-DDE and endosulfan (α + β) were found dominant in both of the fish species. Except endosulfan, and some DDT metabolites, none of the studied organochlorine pesticides was detected in the fish samples. Concentrations of PCBs in anchovy were found higher than those in bonito, whereas DDT and endosulfan concentrations were found similar in both of the fish species. All of the fish samples had residue concentrations below the maximum residue limits (MRL) recommended by FAO/WHO Codex Alimentarius Commission.     

Analysis of the toxicogenomic effects of exposure to persistent organic pollutants (POPs) in Slovakian girls: correlations between gene expression and disease risk

The chemical composition of persistent organic pollutants (POPs) in the environment is not uniform throughout the world, and these contaminants contain many structurally different lipophilic compounds. In a well-defined study cohort in the Slovak Republic, the POP chemicals present in the peripheral blood of exposed children were chemically analyzed. The chemical analysis data revealed that the relative concentration and profile of structurally different organic pollutants, including polychlorinated biphenyls (PCBs), 2,2′-bis(4-chlorophenyl)-1,1-dichloroethylene (p,p′-DDE), 2,2′-bis(4-chlorophenyl)-1,1,1-trichloro-ethane (p,p′-DDT), hexachlorobenzene (HCB) and β-hexachlorocyclohexane (β-HCH), may vary from individual to individual, even within the same exposure area. These chemicals can be broadly classified into two groups. The first group, the PCB congeners, primarily originated from industrial compounds and their byproducts. The second group of compounds originated from or was commonly used in the agricultural sector (e.g., DDT, HCB). The objective of this study was to examine the effects of the two POP exposure profiles on gene expression. For the study population, we selected pre-pubertal girls (mean age of 46.2 ± 1.4 months) with high POP concentrations in their blood (> 75% tile of total POP) and classified them in the high ‘PCB’ group when the total PCB concentration was significantly higher than the total concentration of other POP components and in the ‘Other Than PCB’ (OTP) group, when the total PCB concentration was significantly lower than the concentration of the other major POP constituents. A matched control group of girls (< 25% tile of total POP) was selected for comparison purpose (n = 5 per group). Our aims were to determine whether there were any common effects of high POP exposure at a toxicogenomic level and to investigate how exposure may affect physiological functions of the children in two different exposure scenarios. Global gene expression analysis using a microarray (Affymetrix Gene Chip Human genome U133 Plus 2.0 Array) platform was conducted on the total RNA of peripheral blood mononuclear cells from the girls. The results were analyzed by Partek GS, Louis, MI, which identified twelve genes (ATAD2B, BIVM, CD96, CXorf39, CYTH1 ETNK1, FAM13A, HIRA, INO80B, ODG1, RAD23B, and TSGA14) and two unidentified probe sets, as regulated differentially in both the PCB and OTP groups against the control group. The qRT-PCR method was used to validate the microarray results. The Ingenuity Pathway Analysis (IPA) software package identified the possible molecular impairments and disease risks associated with each gene set. Connective tissue disorders, genetic disorders, skeletal muscular disorders and neurological diseases were associated with the 12 common genes. The data therefore identified the potential molecular effects of POP exposure on a genomic level. This report underscores the importance of further study to validate the results in a random population and to evaluate the use of the identified genes as biomarkers for POP exposure.     

Organohalogen pollutants in herring from the northern Baltic Sea: concentrations, congener profiles and explanatory factors

Organohalogen contaminants were investigated in Baltic herring caught from three catchment areas in the Baltic Sea, off the coasts of Finland. Pools of both small and large herring were analysed for polychlorinated biphenyls (PCB), dibenzo-p-dioxins, dibenzofurans, naphthalenes, camphenes (toxaphene), polybrominated diphenyl ethers and the pesticide DDT and its metabolites. PCB concentrations per fresh weight in small herring were at the same level in all catchment areas, i.e. the Bothnian Bay, the Bothnian Sea and the Gulf of Finland, revealing no hot spots and reflecting most likely long term emissions and atmospheric deposition. Differences in the levels and/or congener profiles of other contaminants between catchment areas may be explained by point sources. Similar concentrations in small and large herring in the Gulf of Finland were possibly due to their common nutrition. In the other areas, differences between small and large herring most likely reflected their different food sources.     

Source emissions and climate change impacts on the multimedia transport and fate of persistent organic pollutants, Chaohu watershed, eastern China

Emission intensity and climate change control the transport flux and fate of persistent organic pollutants (POPs) in multiple environmental compartments. This study applied a multimedia model (BETR model) to explore alternations in the spatio-temporal trends of concentrations and transport flux of benzopyrene (BaP), phenanthrene (Phe), perfluorooctane sulfonates (PFOS) and polychlorinated biphenyls (PCBs) in the Chaohu watershed, located in the lower reaches of the Yangtze River, China in response to changes in source emissions and climate. The potential historic and future risks of these pollutants also were assessed. The results suggest that current trends in concentrations and transport were similar to that of their emissions between 2005 and 2018. During the next 100 years, temporal trends and spatial patterns were not predicted to change significantly, which is consistent with climate change. Based on sensitivity and correlation analyses, climate change had significant effects on multi-media concentrations and transport fluxes of BaP, Phe, PFOS and PCBs, and rainfall intensity was the predominant controlling factor. Risk quotients (RQs) of BaP and Phe-in soil increased from 0.42 to 0.95 and 0.06 to 0.35, respectively, from 2005 to 2090, indicating potential risks. The RQs of the other examined contaminants exhibited little potential risk in soil, water, or sediment. Based on spatial patterns, it was inferred that the ecosystem around Lake Chaohu is the most at risk. The study provides insights needed for local pollution control of POPs in the Chaohu watershed. In addition, the developed approach can be applied to other watersheds world-wide.