Monitoring of persistent organic pollutants (POPs): examples from Lake Vättern, Sweden

Lake V?ttern in southern Sweden is a large oligotrophic lake with high surface to catchment area ratio (ca. 0.4) and a water residence time of 60 years. The lake combines sensitivity to atmospheric POP-pollution with general susceptibility for effects of POPs and slow concentration decline. Time series, from the 1960s until 1996, of PCBs and DDT in fish and data on TCDD in sediment of L. V?ttern are presented and compared to other large lakes. The long time dataset of POPs in Arctic char (Salvelinus salvelinus) shows a significant annual decline of about 5% for PCBs and 13% for DDT. These rates are in agreement with other studies. Nutrients as well as biological effects and factors affecting the fate of POPs in oligotrophic lakes with long residence times are discussed. We propose that oligotrophic clear lakes are important ecosystems for monitoring POPs in biota.     

Predicting logarithmic values of the subcooled liquid vapor pressure of halogenated persistent organic pollutants with QSPR: How different are chlorinated and brominated congeners?

Logarithmic values of the subcooled liquid vapor pressure (log P_L) were estimated for 1436 polychlorinated and polybrominated congeners of benzenes, biphenyls, dibenzo-p-dioxins, dibenzofurans, diphenyl ethers and naphthalenes by employing the Quantitative Structure–Property Relationships (QSPR) approach. The QSPR model developed with GA–PLS technique was characterized by satisfactory goodness-of-fit, robustness and the external predictive performance (R²Y = 0.970, Q_CV² = 0.970, Q_Ext² = 0.966, RMSE_C = 0.21, RMSE_CV = 0.22 and RMSE_P = 0.22). The externally validated model has been applied to predict subcooled liquid vapor pressure of uninvestigated halogenated persistent organic pollutants. Moreover, a simple arithmetic relationship between logarithmic values of subcooled liquid vapor pressures in pairs of chloro- and bromo-analogues has been found. This relationship can be used for estimating log P_L of a brominated compound, whenever log P_L of its chlorinated counterpart is known, without necessity of performing any time-consuming computations.     

Temporal trends of lipophilic persistent organic pollutants in serum from Danish nulliparous pregnant women 2011–2013

The use of the lipophilic persistent organic pollutants (POPs) including polychlorinated biphenyls (PCBs) and several organochlorine pesticides (OCPs) has been prohibited for more than 30 years. In this study, we present the temporal trends of the lipophilic POP serum concentrations in Danish nulliparous pregnant women between 2011 and 2013. We randomly selected 197 pregnant women (gestational age 11–13) from the Aarhus Birth Cohort. The concentrations of the lipophilic POPs in the serum samples were analyzed using gas chromatography. The concentrations were corrected for total serum lipids. The statistical analysis was performed by regression analysis with adjustment for age, BMI, gestational age at blood draw, and smoking status. The serum concentrations of PCB 118, 138, 153, 156, 170, 180, 187, and hexachlorobenzen, trans-nonachlor, β-hexachlorocyclohexane (β-HCH), and p,p’-dichlorodiphenyldichloroethylene were lower in 2013 than in 2011. However, the oxychlordane concentration was lowest in 2011. The serum levels of most lipophilic POPs followed downward trends during the study period, which was expected, as these compounds has been banned for many years. The upward trend of oxychlordane was unexpected and presumably a chance finding.     

Gas–particle partitioning of persistent organic pollutants in the Western Balkan countries affected by war conflicts

Background, aim, and scope  

Bombing and destruction of the industrial and military targets accompanied by complete or incomplete combustion during the war conflict and NATO operation in former Yugoslavia caused the emission of persistent organic pollutants into the atmosphere, water, and soil. A total of 129 ambient air samples from 24 background, urban, and industrial sites, including hot spots, were collected to assess a gas–particle partitioning behavior of various persistent organic pollutants.     

Biomarker responses in European eel (Anguilla anguilla) exposed to persistent organic pollutants. A field study in the Vaccarès lagoon (Camargue, France)

A screening of relevant biomarkers was carried out in order to evaluate metabolic and cellular damages in European eels exposed to a non-point source contamination by persistent organic pollutants (POP) such as polycyclic aromatic hydrocarbons (PAH) and organochlorine compounds (OC) in a protected area, the Nature Reserve of Camargue (France). Investigations were focused on metabolic responses including detoxification mechanisms (biotransformation, antioxidant process), energy requirements and enzymatic membrane markers either involved in neuronal conduction (acetylcholinesterase, AChE) or in osmoregulation and energy metabolism (ATPases). The hepatic and muscular glycogen rates seemed to be suitable biomarkers as well as three hepatic activities involved in the protection against oxyradicals: catalase, glutathione peroxidase (SeGPx) and superoxide dismutases (SOD). The muscle and gill ATPases as well as the muscle and brain AChE showed more significant relevance in terms of biomarkers than the biotransformation enzymes: ethoxyresorufine-O-deethylase (EROD) and uridine diphospho-glucuronyl transferase (UDPGT). However, most of these enzymatic activities depend on numerous abiotic factors, which must be taken into account in such a biomarker assessment approach. Our study provides some conclusive elements to approve the use in situ of biomarkers developed from laboratory studies. It also raises a question regarding the location of contaminant impregnation in fish organ, in relation with age, development status or mode of contamination, and its influence on biomarker response. If the relevance of membrane indicators is confirmed, this study provides an original statement of the extent of the ecotoxicological threat for the aquatic species in a protected area, due to the occurrence of POP in the cell membranes.     

An exposure to endocrine active persistent pollutants and endometriosis — a review of current epidemiological studies

Environmental Science and Pollution Research - Widespread exposure to persistent pollutants can disrupt the bodies’ natural endocrine functions and contribute to reproductive diseases like...     

Historical trends in persistent organic pollutants and metals recorded in sediment from Lake Ellasjøen, Bjørnøya, Norwegian Arctic

Ellasj?en receives contaminants from both atmospheric and biological transport (seabird guano). Historical trends of selected persistent organic pollutants and metals were determined by interpretation of down-core contaminant profiles in conjunction with sediment layer ages, determined by the (210)Pb method. Polychlorinated biphenyls (PCBs) and dichloro-diphenyl-trichloroethane and metabolites (DDTs) increased from about 1930 until 1970 (max. sum PCBs 71.8 ng/g dry weight (dw), max sum DDTs 4.0 ng/g dw), declining afterwards to 46.4 ng/g dw and 1.6 ng/g dw, respectively. Polybrominated diphenylethers (PBDEs) concentrations are increasing in Ellasj?en, reaching 0.73 ng/g dw in 2001. Hexabromocyclododekane (HBCD) was measured only in sediment from 1-2 cm depth (0.43 and 3.88 ng/g dw of alpha- and gamma-HBCD, respectively). Most metals (As, Cd, Co, Ni and Zn) showed a similar pattern as PCBs. No clear trends were observed for Cr, Pb or V. Mercury (Hg) has increased gradually since the beginning of the industrial era.     

Persistent organic pollutants associated to water fluxes and sedimentary processes in the Colorado River delta, Baja California, México

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were studied in sediment cores from two distinctive modern channels of the Colorado River (CR) delta. Their abundance and temporal changes are associated with flood-flows from the CR across the USA-Mexico border. The CR channel is directly exposed to river flood-flows while the Hardy River (HR) is a local channel derived mainly from agricultural runoff, geothermal effluents, and treated urban wastewater. Different headwater compositions and degrees of exposure to flood-flows appear to be the factors controlling the composition of persistent organic pollutants (POPs). Enrichment of OCPs (46 ng g⁻¹ dwt in HR and 4.37 ng g⁻¹ dwt in CR) occurred during or a few years after flooding. PCB-138 (4.2 ng g⁻¹ dwt) is enriched in HR suggesting its origin in dielectric oils from the geothermal power plant. PCB-28 (2.1 ng g⁻¹ dwt) in CR may be related with atmospheric input and/or re-deposition of upstream sediments. In surficial sediments (0-3 cm), only HR exceeds international sediment quality guidelines (4,4′-DDE = 8.16 ng g⁻¹ dwt and ΣDDT = 8.34 ng g⁻¹ dwt).     

Much Ado: How Big Is the Problem of Hydrolysis of Methyl Tertiary Butyl Ether (MtBE) to Form Tertiary Butyl Alcohol (tBA)?

Groundwater contaminated by the gasoline additive methyl tertiary butyl ether (MtBE) is also frequently impacted by tertiary butyl alcohol (tBA). The USEPA recently sponsored a study that discusses the possibility of hydrolysis of MtBE to form tBA during analytical procedures. This finding is important because it suggests that existing tBA data may not accurately depict tBA or MtBE concentrations in groundwater. This article discusses the mechanism and kinetics of MtBE hydrolysis, then presents three case studies of analytical results from sites in California, USA. Although these case studies are limited in scope, the data do not support the occurrence of the hydrolysis of MtBE to form tBA due to acid preservation of groundwater samples. At a minimum, this suggests that MtBE hydrolysis may not be as pervasive a problem as suggested in USEPA's study; therefore, concerns about the validity of historical tBA data may not be warranted. The reason for this result may be simple: there are two necessary factors that promote hydrolysis: low pH and high temperature (above 40°C). Although the static headspace analysis method used to obtain the data in the White et al. study may require heating to achieve adequate sensitivity, many laboratories perform purge-and-trap analyses without heating. Under those conditions, hydrolysis may not occur. However, it may be prudent to preserve samples with alkaline preservatives, to eschew high temperatures during the analysis of groundwater samples, or to neutralize the sample pH before heating.     

EU Water Framework Directive and Stockholm Convention Can we reach the targets for priority substances and persistent organic pollutants?

Background, aim and scope  

Water is a renewable resource and acceptable quality is important for human health, ecological and economic reasons, but human activity can cause great damage to the natural aquatic environment. Managing the water cycle in a sustainable way is the key to protect natural resources and human health. On a global level, the microbiological contamination of water sources is a major problem in connection with poverty and the United Nations Millennium Development Declaration is an important initiative to handle this problem. In terms of environmental health, persistent organic pollutants (POPs) circulate globally; as they travel long distances, they are found in remote areas far from their original source of application and can cause damage wherever they move to. On a global scale, United Nations Environmental Programme (UNEP) issued the Stockholm Convention to reduce POPs; in the European Union (EU), one intention of the Water Framework Directive (WFD) is to reach the good chemical status of waters; beside these regulations, there are other directives in support of these goals. The aim of this paper is to discuss whether the Stockholm Convention and the WFD allows meeting the targets of protection of human and environmental health, which are established in the different directives and how could we approach the targets.     

The deep-sea as a final global sink of semivolatile persistent organic pollutants? Part I: PCBs in surface and deep-sea dwelling fish of the north and south Atlantic and the Monterey Bay Canyon (California)

The understanding of the global environmental multiphase distribution of persistent organic pollutants (POPs) as a result of the physico-chemical properties of the respective compounds is well established. We have analysed the results of a vertical transport of POPs from upper water layers (0-200 m) to the deepwater region (> 800 m) in terms of the contamination of the biophase in both water layers. The contents of persistent organochlorine compounds like polychlorinated biphenyls (PCBs) in fish living in the upper water layers of the North Atlantic and the South Atlantic, and at the continental shelf of California (Marine Sanctuary Monterey Bay and its deep-sea Canyon) are compared to the levels in deep-sea or bottom dwelling fish within the same geographic area. The deep-sea biota show significantly higher burdens as compared to surface-living species of the same region. There are also indications for recycling processes of POPs--in this case the PCBs--in the biophase of the abyss as well. It can be concluded that the bio- and geo phase of the deep-sea may act similarly as the upper horizons of forest and grasslands on the continents as an ultimate global sink for POPs in the marine environment.     

The deep-sea as a final global sink of semivolatile persistent organic pollutants? Part II: Organochlorine pesticides in surface and deep-sea dwelling fish of the north and south Atlantic and the Monterey Bay Canyon (California)

The understanding of the global environmental multiphase distribution of persistent organic pollutants (POPs) as a result of the physico-chemical properties of the respective compounds is well established. We have analysed the results of a vertical transport of POPs from surface water to deepwater in terms of the contamination of the biota living in the respective environmental compartments. Samples were taken from the North and the South Atlantic and from the uprising water region of the continental shelf of California (Marine Sanctuary Monterey Bay and its Canyon). The contents of persistent organochlorine pesticides (DDTs, chlordanes, toxaphenes, HCHs, and HCB) in surface-living fish are compared to those in deepwater fish of the same geographic area. The deepwater biota show significantly higher burdens as compared to surface-living species of the same region. There are also indications for recycling processes of POPs of the class of organochlorine pesticides in the biophase of the abyss as well. It can be concluded that the bio- and geophase of the deep-sea may act as an ultimate global sink for persistent semivolatile contaminants in the marine environment like the soil on the continents.     

Fluorescence excitation–emission matrix spectra coupled with parallel factor and regional integration analysis to characterize organic matter humification

The present several humification indexes cannot provide the whole fluorescence information on organic matter composition and the evaluation results from them are inconsistent sometimes. In this study, fluorescence excitation–emission matrix spectra coupled with parallel factor analysis and fluorescence regional integration analysis were utilized to investigate organic matter humification, and the projection pursuit cluster (PPC) model was applied to form a suitable index for overcoming the difficulties in multi-index evaluation. The result showed that the ratio between the volume of humic- and fulvic-like fluorescence region and the volume of protein-like fluorescence region not only revealed the heterogeneity of organic matter, but also provided more accurate information on organic matter humification. In addition, the results showed that the PPC model could be used to characterize integrally the humification, and the projected characteristic value calculated from the PPC model could be used as the integrated humification evaluation index.     

Polychlorinated camphenes (toxaphenes), polybrominated diphenylethers and other halogenated organic pollutants in glaucous gull (Larus hyperboreus) from Svalbard and Bjørnøya (Bear Island)

The levels of polychlorinated camphenes (toxaphenes) were investigated in liver samples from 18 glaucous gulls (Larus hyperboreus) from Bj?rn?ya (74 degrees N, 19 degrees E) and four individuals from Longyearbyen (78 degrees N, 15 degrees E). Additionally brominated flame retardants (BFRs), PCBs and chlorinated pesticides were investigated in liver and intestinal contents of 15 of the glaucous gulls from Bj?rn?ya. Of the analysed BFRs only 2,2',4,4'-tetra- and 2,2',4,4',5-pentabrominated diphenylethers (PBDE 47 and 99) could be detected. The concentrations ranged between 2 and 25 ng/g ww. In addition, high resolution measurements with GC/HRMS revealed the existence of several, not quantified, PBDEs and polybrominated biphenyls (PBBs) congeners in the samples. B9-1679 and B8-1413 were the dominating toxaphenes with median concentrations of 8 and 15 ng/g ww. Concentrations of toxaphenes and PBDEs were up to 100-times lower than the concentrations of PCB and some of the pesticides. PCB and p,p/-DDE constituted 90% of the contaminants found.     

Bioavailability of pollutants sets risk of exposure to biota and human population in reservoirs from Iguaçu River (Southern Brazil)

Environmental Science and Pollution Research - The Iguaçu River, located at the Southern part of Brazil, has a great socioeconomic and environmental importance due to its high endemic fish...     

How contaminated with ammunition-derived lead is meat from European small game animals? Assessing and reducing risks to human health

Small game animals are generally hunted with lead gunshot which often fragments causing elevated lead concentrations in meat and presenting health risks to frequent consumers and vulnerable groups. We reviewed three decades of European data on lead concentrations in the meat of gamebirds, rabbits and hares across countries with various restrictions on lead gunshot use. Mean meat lead concentrations decreased to a low level in Denmark, the only country in the study with a total ban on lead gunshot use. In contrast, elsewhere in Europe meat lead concentrations increased over time, an unexplained and previously undescribed finding. The only regulatory restriction associated with a decrease in meat lead concentrations was the Danish total ban on lead gunshot use. We calculated an arithmetic mean lead concentration in small game meat of 5.205 ppm w.w. (2011–2021) from across Europe. EU and UK regulators are considering banning lead ammunition for all hunting to protect human and wildlife health. The mean value we found for small game meat (2011–2021) was fourteen times higher than that used in a recent EU-wide risk assessment.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-022-01737-9.