Introducing an integrated climate change perspective in POPs modelling, monitoring and regulation

This paper presents a review on the implications of climate change on the monitoring, modelling and regulation of persistent organic pollutants (POPs). Current research gaps are also identified and discussed.Long-term data sets are essential to identify relationships between climate fluctuations and changes in chemical species distribution. Reconstructing the influence of climatic changes on POPs environmental behaviour is very challenging in some local studies, and some insights can be obtained by the few available dated sediment cores or by studying POPs response to inter-annual climate fluctuations. Knowledge gaps and future projections can be studied by developing and applying various modelling tools, identifying compounds susceptibility to climate change, local and global effects, orienting international policies.Long-term monitoring strategies and modelling exercises taking into account climate change should be considered when devising new regulatory plans in chemicals management.     

Linking molecular interactions to consequent effects of persistent organic pollutants (POPs) upon populations

There is great concern about the potential adverse effects of persistent organic pollutants (POPs) on wildlife. Threats come from toxic chemicals with long half lives in the environment that were released worldwide on a large scale in the past, at a time when little was known of their potential effects on the environment. Although the Stockholm Convention (2001) initially targeted 12 POP chemicals--organochlorinated compounds--for the reduction/elimination of releases, the problem can be extended to persistent toxic substances more generally. Therefore, identifying early biomarkers for possible toxic effects to populations in the long term is a challenge for ecotoxicologists. Regional decline in fish, bird and/or invertebrate populations resulting from exposure to POPs, such as DDT (dichlorodiphenyltrichloroethane), PCBs (polychlorinated biphenyls), PCDD (polychlorinated dibenzo-p-dioxins), and TBT (tributyltin) could be related to some biochemical, endocrine and physiological effects in individuals. Examples of known mechanisms of POP ecotoxicity will be illustrated in the first part. The next parts will be devoted to (i) data gaps and limitations to extrapolation from lower to higher levels of biological organization, (ii) confusing factors in field studies and the combined effects of persistent toxic pollutants and (iii) recommendations for the design and interpretation of experimental studies.     

Geospatial patterns of hospitalization rates for stroke with comorbid hypertension in relation to environmental sources of persistent organic pollutants: results from a 12-year population-based study

Purpose  

Recent evidence indicates that exposure to persistent organic pollutants (POPs) is emerging as an important risk factor for atherosclerosis-related diseases, including stroke. Hypertension (HTN) is a major risk factor for stroke, and some studies suggest that exposure to POPs is also a risk factor for HTN. We hypothesized that POPs increase the environmental burden of stroke with comorbid HTN.     

Climate change influence on POPs distribution and fate: a case study

Climate change has the potential of affecting the behaviour and distribution of organic pollutants, including POPs. Direct effects of climate change, like temperature increase, modification of wind and precipitation patterns, sea level rise, snow and ice cover, may be very effective in altering the partitioning of POPs among the environmental compartments. Other consequences of future climate scenarios may imply the alteration of degradation rates, soil properties (and hence land use), air-particle partitioning of chemicals and so forth. A case study is here presented to illustrate the major implications of climate change on the long term at the local scale. A dynamic multimedia model was applied to selected PCB and PCDD/F congeners to simulate the effects of climate change on their distribution and fluxes over the next 50 y in the Venice Lagoon (Italy). Different climate change scenarios were tested, finding noticeable variations in POPs concentration even for minor environmental changes. PCBs and PCDFs environmental concentrations may differ by a factor two in a moderate climate change scenario, compared to a situation with stable climate over the next 50 y. However, model results also suggest that if global warming may have the potential of reducing the environmental levels of these chemicals, it would probably enhance their mobility and hence their potential for long range atmospheric transport.     

Coupled mother-child model for bioaccumulation of POPs in nursing infants

Bioaccumulation of persistent organic pollutants (POPs) leads to high levels in human milk and high doses of POPs for nursing infants. This is currently not considered in chemical risk assessment. A coupled model for bioaccumulation of organic chemicals in breast-feeding mother and nursing infant was developed and tested for a series of organic compounds. The bioaccumulation factors (BAFs) in mother, breast milk and child were predicted to vary with log K_OW and, for volatile compounds, with K_AW and concentration in air. The concentrations of POPs in the infant body increase the first half year to about factor 3 above mother and decline thereafter to lower levels. The predicted results are close to empirical data and to an empirical regression. The new mother–child model is compact due to its easy structure and the analytical matrix solution. It could be added to existing exposure and risk assessment systems, such as EUSES.     

Long-range transport and global fractionation of POPs: insights from multimedia modeling studies

The long-range transport of persistent organic pollutants (POPs) is investigated with two multimedia box models of the global system. ChemRange is a purely evaluative, one-dimensional steady-state (level III) model; CliMoChem is a two-dimensional model with different temperatures, land/water ratios and vegetation types in different latitudinal zones. Model results are presented for three case studies: (i) the effect of atmospheric aerosol particles on the long-range transport of POPs, (ii) the effect of oceanic deposition on the long-range transport of different PCB congeners, (iii) the global fractionation of different PCB congeners. The model results for these case studies show: (i) the low atmospheric half-lives estimated for several organochlorine pesticides are likely to be inconsistent with the observed long-range transport of these compounds; (ii) export to the deep sea reduces the potential for long-range transport of highly hydrophobic compounds (but does not remove these chemicals from the biosphere); (iii) there are different meanings of the term global fractionation that refer to different aspects of the fractionation process and need to be distinguished. The case-study results further indicate that the influences of varying environmental conditions on the physicochemical properties and the degradation rate constants of POPs need to be determined.     

Dioxin-like activity in environmental and human samples from Greenland and Denmark

Dioxins and dioxin-like (DL) compounds are some of the most toxic chemicals being highly persistent in the environment. The toxicological effects of dioxins are mediated via the aryl hydrocarbon receptor (AhR). Compounds of diverse structure and lipophility can bind and activate AhR. The AhR transactivation bioassay is utilized in an array of projects to study the AhR-mediated activities of individual chemicals and mixtures and for epidemiological purposes.This review summarizes a series of studies regarding the DL-activity of single compounds and complex compound mixtures in the environment and humans.We found that some pesticides, plasticizers and phytoestrogens can activate the AhR, and the combined effect of compounds with no or weak AhR potency cannot be ignored.The significant DL-activity in the wastewater effluent indicates the treatment is not sufficient to prevent contamination of surface waters with dioxins. Our results from human studies suggest that the serum DL-activity reflect the complex mixture of persistent organic pollutants (POPs). Greenlandic Inuit had lower serum DL-activity level compared to Europeans, probably due to long distance from the dioxin sources and UV degradation of the high potent dioxin and/or the inhibitory effect of the high level of non-DL POPs. Selective bioaccumulation of PCBs in the food chain may contribute to the negative correlation between serum POPs and DL-activity observed in Greenlandic Inuit.Hence the AhR transactivation bioassay provides a cost-effective and integrated screening tool for measurement of the DL-activity in human, environmental and commercial samples.     

The spatial scale of organic chemicals in multimedia fate modeling. Recent developments and significance for chemical assessment

In the last years, the spatial range (SR) or characteristic travel distance (CTD) of organic chemicals has found increasing scientific interest as an indicator of the long-range transport (LRT) potential and, in combination with persistence, as a kind of 'hazard' indicator on the exposure level. This development coincides with European debates about more effective and more preventive approaches to the chemicals assessment, and about an international, legally-binding instrument for the phase out of persistent organic pollutants (POPs). Persistence and LRT potential are important issues in these debates. Here, the development of the concept of assessing the spatial scale from early ideas in the 1970s and 1980s to recent studies in the field of multimedia fate and transport modeling is summarized. Different approaches to the modeling of environmental transport (advective and dispersive) and different methods for quantifying the SR or CTD are compared. Relationships between SR or CTD and different persistence measures are analyzed. Comparison of these relationships shows that conclusions for chemical assessment should be based on an evaluation of different persistence and spatial scale measures. The use of SR or CTD and persistence as hazard indicators in the chemicals assessment is illustrated.     

Multi-biomarker responses in green mussels exposed to PFCs: effects at molecular,cellular, and physiological levels

Perfluorinated chemicals (PFCs) are extremely persistent and have been found extensively in the environment and wildlife. Oceans are the final sink for many persistent organic pollutants (POPs) including PFCs. However, to date, there has been a lack of studies that investigated the environmental consequences of PFCs on marine organisms. To fill in this gap, environmental toxicity of two dominant PFCs, perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA), was examined in a sentinel species, green mussel Perna viridis, using a series of biomarkers corresponding to different biological levels (molecular, cellular, and physiological). Correlations among these biomarkers were also investigated. The results showed that the tested compounds can induce a series adverse effect at different biological levels, including oxidative stress, DNA damage, membrane instability, suppressed filtration rate, and reduced body weight. Correlation analysis revealed that excess production of reactive oxygen species could be the major toxic pathway. An indirect mode of toxic action was also explored where adverse impacts could be secondary effects of PFC exposure. The joint analysis of biomarkers from multiple biological levels resulted in a comprehensive understanding of how PFC exposure can influence the health of organisms. The correlations of these biomarkers also provided a new perspective of the ecological consequences of PFCs.     

Exposure patterns of UV filters, fragrances, parabens, phthalates, organochlor pesticides, PBDEs, and PCBs in human milk: correlation of UV filters with use of cosmetics

In order to assess potential risks of exposure to environmental chemicals, more information on concomitant exposure to different chemicals is needed. We present data on chemicals in human milk of a cohort study (2004, 2005, 2006) of 54 mother/child pairs, where for the first time, cosmetic UV filters, synthetic musks, parabens and phthalate metabolites were analyzed in the same sample along with persistent organochlor pollutants (POPs), i.e., organochlor pesticides and metabolites, polybrominated diphenylethers and polychlorinated biphenyls (PCBs). The two groups of chemicals exhibited different exposure patterns. Six out of seven PCB congeners and a majority of pesticides were present in all milk samples, with significant correlations between certain PCB congener and pesticide levels, whereas the cosmetic-derived compounds, UV filters, parabens and synthetic musks, exhibited a more variable exposure pattern with inter-individual differences. UV filters were present in 85.2% of milk samples, in the range of PCB levels. Comparison with a questionnaire revealed a significant correlation between use of products containing UV filters and their presence in milk for two frequently used and detected UV filters, 4-methylbenzylidene camphor and octocrylene, and for the whole group of UV filters. Concentrations of PCBs and organochlor pesticides were within ranges seen in Western and Southern European countries. For several POPs, mean and/or maximum daily intake calculated from individual concentrations was above recent US EPA reference dose values. Our data emphasize the need for analyses of complex mixtures to obtain more information on inter-individual and temporal variability of human exposure to different types of chemicals.     

Fifteen years of monitoring of POPs in the breast milk, Czech Republic, 1994–2009: trends and factors

Background, aim and scope

The breast milk has been recommended to carry out as a monitoring tool for effectiveness evaluation of the Stockholm Convention on Persistent Organic Pollutants (POPs). Polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloro-ethane (DDT) and its metabolites (DDX), hexachlorbenzene (HCB) and isomers of hexachlocyklohexane (HCHs) have been monitored in the breast milk of nursing mothers in the Czech Republic since 1994 as a part of The Environmental Health Monitoring System. Knowledge about long-term POPs distribution and accumulation in the human body is crucial to understanding uptake, degradation and subsequent effects as well as to conduct risk assessments. The main aim of this study is to evaluate 15-years long-term trends of selected POPs in human milk in the Czech Republic and to elucidate the questionnaire information about the age, parity and social habits, to the final concentrations. This effectiveness evaluation of POPs restriction is quite precisely after 15-years monitoring campaigns.

Materials, methods and results

The human milk samples (4,753 samples) were analysed for a number of chlorinated organic chemicals including PCBs and selected chlorinated pesticides (OCPs, HCB, HCHs, DDX). The relative change of concentration per year for all chemicals was analysed. The remaining percentages of POPs in breast milk in comparison to 1994 are also expressed. Czech population half-lives of POPs in breast milk, derived from either linear or exponential models were computed.

Conclusions and perspectives

The long-term data indicates a continuation of a decreasing trend of POPs concentrations on breast milk. Our study did not confirm lactation and parity as an important outflux resulting in the decrease in concentrations in mothers, which is in the antagonism with most of the studies. The higher BMI was associated with higher amounts of HCB and lower amounts of higher chlorinated PCBs. The results confirm the effectiveness of restrictions of POPs usage in the Czech Republic. This ongoing long-term study is very useful tool for parametric effectiveness evaluation of Stockholm Convention.     

Neurobehavioral deficits and brain oxidative stress induced by chronic low dose exposure of persistent organic pollutants mixture in adult female rat

Persistent organic pollutants (POPs) are long-lived organic compounds that are considered one of the major risks to ecosystem and human health. Recently, great concerns are raised about POPs mixtures and its potential toxicity even in low doses of daily human exposure. The brain is mostly targeted by these lipophilic compounds because of its important contain in lipids. So, it would be quite interesting to study the effects of exposure to these mixtures and evaluate their combined toxicity on brain cells. The present study was designed to characterize the cognitive and locomotors deficits and brain areas redox status in rat model. An orally chronic exposure to a representative mixture of POPs composed of endosulfan (2.6 μg/kg), chlorpyrifos (5.2 μg/kg), naphthalene (0.023 μg/kg) and benzopyrane (0.002 μg/kg); the same mixture with concentration multiplied by 10 and 100 was also tested. Exposed rats have shown a disturbance of memory and a decrease in learning ability concluded by Morris water maze and the open field tests results and anxiolytic behaviour in the test of light/dark box compared to control. Concerning brain redox homeostasis, exposed rats have shown an increased malondialdehyde (MDA) amount and an alteration in glutathione (GSH) levels in both the brain mitochondria and cytosolic fractions of the cerebellum, striatum and hippocampus. These effects were accompanied by a decrease in levels of cytosolic glutathione S-transferase (GST) and a highly significant increase in superoxide dismutase (SOD) and catalase (CAT) activities in both cytosolic and mitochondrial fractions. The current study suggests that environmental exposure to daily even low doses of POPs mixtures through diet induces oxidative stress status in the brain and especially in the mitochondria with important cognitive and locomotor behaviour variations in the rats.     

Exposure to persistent organic pollutants in utero and related maternal characteristics on birth outcomes: a multivariate data analysis approach

Persistent organic pollutants (POPs) have the capacity to pass through the placental barrier and into the fetal blood stream, and pose health risks to fetuses and neonates who are believed to be more vulnerable to the effects of environmental pollutants. In this study, the prevalence of POPs, including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs), were determined in 41 cord blood samples collected during the year 2006 in Singapore. The effects of these xenobiotics and the maternal characteristics on fetal growth and development were explored using multivariate data analysis (MVA) techniques, including partial least-squares regression (PLSR) and discriminant analysis (PLS-DA). POPs were found in all cord blood samples, corroborating the transplacental transfer (TPT) of these xenobiotics. Chlordanes and PCBs were observed to have adverse effects on fetal growth (i.e. birth weight, length, head circumference) and health (as indicated by Apgar scores), indicating the chemical exposure in utero could also be deemed as an influential factor on fetal growth, even at the normal doses in general population. Maternal height, weight, ethnicity, dietary habits and lifestyle were also the determinants for the neonatal variables. Exposure to POPs may alter maternal hormone levels, which could regulate the offspring sex. Trans-chlordane, p,p'-DDE, p,p'-DDT and PCB 138 and 158 were speculated as testosterone triggers which lead to more baby boys, while the effects of beta-HCH and PCB 180 were opposite.     

A preliminary investigation of persistent organic pollutants in ambient air in Hong Kong

Air samples were collected for characterisation of PCDD/Fs and other persistent organic pollutants (POPs) such as aldrin, alpha-HCH, beta-HCH, delta-HCH, gamma-HCH, o,p'-DDT, p,p'-DDT, o,p'-DDE, p,p'-DDE, o,p'-DDD, p,p'-DDD, dieldrin, endrin, endosulfan I and II, heptachlor, heptachlor epoxide and hexachlorobenzene during the winter of 2000/2001 at the weather station of the Hong Kong Observatory at Tai Mo Shan (TMS), which is the highest point (approximately 957 m) in Hong Kong, besides the routine monitoring of PCDD/Fs and 200 other toxic air pollutants (TAPs) at two urban TAPs stations at Tsuen Wan and Central & Western. Concentrations of the pollutants detected at TMS station were evaluated and compared to those recorded at the urban stations. Though pesticides including alpha-HCH, hexachlorobenzene, DDT, DDE, heptachlor, and endosulfan I were detected, these pesticides were found at relatively low concentrations of about 0.02-0.23 ng/m3 and should not have any significant health effects. Concentrations of some of the monitored POPs were found to be higher whilst most of the monitored TAPs were at comparable levels to those measured at the urban stations during the same period. According to the Stockholm Convention on POPs (May 2001), the 12 chemicals labelled by the United Nations as the most dangerous are: aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, mirex, toxaphene, hexachlorobenzene, PCBs and dibenzo-p-dioxins/dibenzofurans (PCDDs)/(PCDFs). Given that there has not been any large scale use of organo-chlorine pesticides recorded since the decline of local farming activities in recent years, the results of the present study again show that pesticides and POPs such as PCDDs/PCDFs are ubiquitous environmental contaminants present in the atmosphere of Hong Kong. The findings also indicate that organo-chlorine pesticides and PCDDs/PCDFs are among the most prevalent chlorinated semi-volatile pollutants present in Hong Kong. Results obtained in the present study suggest that selected pesticides may be used as tracers for transport of pollutants for regional air quality study.     

Exposure of ruminants to persistent organic pollutants and potential of decontamination

Human activities are emitting persistent organic pollutants (POPs) to the environment. These compounds have raised concerns about the risk of transfer through the food chain via animal products. They are characterized by a strong persistence in environmental matrices and a lipophilicity which may lead to their accumulation in fat tissues. In EU Regulations (no. 1881/2006, 1259/2011), maximum acceptable levels for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs), and dioxin-like or nondioxin-like polychlorinated biphenyls (PCBs) in food of animal origin have been set. Transfer rates from contaminated fodder to milk have been established: for PCBs, the rate of transfer varies from 5 to 90 % and for PCDD/Fs from 1 to 40 %. The differential transfer of the compounds towards milk is related to the hydrophobicity of the pollutants and to their metabolic susceptibility. According to numerous authors, soil is the major reservoir for POPs, and its involuntary ingestion by farm animals reared outdoors may be the main cause of animal product contamination (meat, milk, or eggs). Recent studies seem to indicate that soil is a real risk matrix in terms of transfer of pollutants to the food chain. A POP crisis management is extremely difficult, since it impacts many farmers located in the contaminated area. The question arising is to know if livestock contaminated by POPs may be decontaminated and further used for their initial purpose. Recent data demonstrate that the decontamination process appear feasible and depends on initial level of contamination or the physiological status of the animals.     

The carcinogenic risk of some organic vapors indoors: A theoretical survey

This exploratory report examines the risk of selected organic air pollutants measured in homes in the United States and the Netherlands. After several theoretical assumptions, estimates are made for the carcinogenic potency of each chemical; combined with the exposure measurements these give estimates of cancer risk. These estimates are compared with risks of these same pollutants outdoors and in drinking water and also with other well known indoor air pollutants: cigarette smoke, radon gas and formaldehyde. These comparisons indicate priorities for action. Some suggestions are made for future studies.     

Reliable QSAR for estimating Koc for persistent organic pollutants: correlation with molecular connectivity indices

Several recent studies have shown that n-octanol/water partition coefficients may not be a good predictor for estimating soil sorption coefficients of persistent organic pollutants (POPs), defined here as chemicals with log Kow greater than 5. Thus, an alternative QSAR model was developed that seems to provide reliable estimates for the soil sorption coefficients of persistent organic pollutants. This model is based on a set of calculated molecular connectivity indices and evaluated soil sorption data for 18 POPs. The chemical's size and shape, quantified by 1chi, 3chiC and 4chiC(v) indices, have a dominant effect on the soil sorption process of POPs. The developed QSAR model was rationalized in terms of potential hydrophobic interactions between persistent organic pollutants and soil organic matrix. Its high predictive power has been verified by an extensive internal and external validation procedure.     

Air Pollution Research Needs: Herbaceous and Ornamental Plants and Agriculturally Generated Pollutants

Effects of various air pollutants on economically important crops and ornamentals have been studied since before the turn of the century.

Summaries of this research on the effects of air pollutants, that have appeared in criteria documents developed by the Environmental Protection Agency, should be reviewed with respect to differences in plant susceptibility found in various regions of the country. These susceptibility differences are associated with variations in both environmental conditions and distribution of pollutants. Research efforts on air pollution injury to vegetation have often been poorly coordinated leaving many gaps in our knowledge. A better assessment of the impact of air pollution on vegetation is required to attain realistic controls for pollutants affecting agriculture. Research areas of major concern include: baseline information on effects of pollutants on agricultural productivity; dose-response information to support predictive mathematical models for acute and chronic studies of growth, yield, and quality effects; effects of pollutants interacting with other pollutants and with insects and plant diseases; mechanisms of pollutant action; genetic changes related to pollutant effects; effects of environmental stresses on plant response to pollutants; evaluation of plants including soil microbes as pollutant sinks; development of techniques to minimize pollutant effects; and, the effects of agricultural chemicals as air pollutants. There is a need for studies that consider the whole plant in its natural environment. Conceptual models interrelating pollutant effects and their interactions and ultimately mathematical models will be needed to develop an intelligent approach to land management. The effects of agriculturally produced pollutants on plants and other receptors must be identified and quantified.     

Man-made chemicals found in remote areas of the world: the experimental definition for POPs

Members of the United Nations Economic Commission for Europe (UN-ECE) signed a legally binding protocol on persistent organic pollutants (POPs) in February 1998 under the Convention on Long-Range Transboundary Air Pollution. A treaty that intends to control the production, import, export, disposal and use of toxic chemicals that persist for decades in the environment has been formally signed at a conference in May 2001 in Stockholm. The 2001 POP treaty, like the 1998 LRTAP POP protocol, contains a provision on adding further chemicals to the initial group of twelve or fifteen. The occurrence of a compound or a group of compounds in so called remote and pristine areas, e.g. in the Artic or in the Southern Hemisphere, proves its stability under the chemical and biological conditions of the environment. Compounds identified in this way, in samples taken primarily in very remote regions of the planet, are classified by their environmental fate and global distribution as persistent organic pollutants (POPs), regardless of any political assessments.