Time trend of exposure to dechloranes: Plasma samples of German young adults from the environmental specimen bank collected from 1995 to 2017.

Dechloranes, like Dechlorane Plus® are commonly used flame retardants identified by the EU as substances of very high concern (SVHC) because of their persistence and bioaccumulation potential. To characterize the dechlorane exposure of Germans in the last two decades, 180 archived blood plasma samples of the German Environmental Specimen Bank (students aged 20-29 years) collected at six time points between 1995 and 2017 were analyzed for four dechloranes; namely Dechlorane Plus® (syn- and anti-DDC-CO), dechlorane 602 (DDC-DBF), and dechlorane 603 (DDC-Ant). These were quantified using a GC-MS/MS method. Overall, anti- and syn-DDC-CO were detected in 88% and 98% of the samples, whereas DDC-DBF and DDC-Ant were found in 40% and 37% of the samples, respectively. The median (95th percentile) values were 1.0 ng/g lipid weight (l.w.) (3.0 ng/g l.w.). for anti-DDC-CO, 0.6 ng/g l.w (1.9 ng/g l.w.). for syn-DDC-CO, 0.1 ng/g l.w (0.6 ng/g l.w.). for DDC-DBF, and 0.1 ng/g l.w (0.2 ng/g l.w.). for DDC-Ant. The 95th percentile concentrations of the sum of syn- and anti-DDC-CO decreased from 4.2 ng/g l.w. in 1995, to 2.9 ng/g l.w. in 1999, and subsequently increased to 3.7 ng/g l.w. in 2008, and up to 5.9 ng/g l.w. in 2017. A statistically significant decrease with time was observed for DDC-DBF and DDC-Ant, but not for DDC-CO. Our medians found in blood samples in 2017 are similar to those observed in Germany in 2013/14, but higher compared to values reported in other European countries. Overall, more toxicological and monitoring data is needed to better characterize the potential impact on health.

Heavy metal pollution and co-selection for antibiotic resistance: A microbial palaeontology approach.

Frequent and persistent heavy metal pollution has profound effects on the composition and activity of microbial communities. Heavy metals select for metal resistance but can also co-select for resistance to antibiotics, which is a global health concern. We here document metal concentration, metal resistance and antibiotic resistance along a sediment archive from a pond in the North West of the United Kingdom covering over a century of anthropogenic pollution. We specifically focus on zinc, as it is a ubiquitous and toxic metal contaminant known to co-select for antibiotic resistance, to assess the impact of temporal variation in heavy metal pollution on microbial community diversity and to quantify the selection effects of differential heavy metal exposure on antibiotic resistance. Zinc concentration and bioavailability was found to vary over the core, likely reflecting increased industrialisation around the middle of the 20th century. Zinc concentration had a significant effect on bacterial community composition, as revealed by a positive correlation between the level of zinc tolerance in culturable bacteria and zinc concentration. The proportion of zinc resistant isolates was also positively correlated with resistance to three clinically relevant antibiotics (oxacillin, cefotaxime and trimethoprim). The abundance of the class 1 integron-integrase gene, intI1, marker for anthropogenic pollutants correlated with the prevalence of zinc- and cefotaxime resistance but not with oxacillin and trimethoprim resistance. Our microbial palaeontology approach reveals that metal-contaminated sediments from depths that pre-date the use of antibiotics were enriched in antibiotic resistant bacteria, demonstrating the pervasive effects of metal-antibiotic co-selection in the environment.

Lead pollution recorded in Greenland ice indicates European emissions tracked plagues, wars, and imperial expansion during antiquity.

Lead pollution in Arctic ice reflects midlatitude emissions from ancient lead-silver mining and smelting. The few reported measurements have been extrapolated to infer the performance of ancient economies, including comparisons of economic productivity and growth during the Roman Republican and Imperial periods. These studies were based on sparse sampling and inaccurate dating, limiting understanding of trends and specific linkages. Here we show, using a precisely dated record of estimated lead emissions between 1100 BCE and 800 CE derived from subannually resolved measurements in Greenland ice and detailed atmospheric transport modeling, that annual European lead emissions closely varied with historical events, including imperial expansion, wars, and major plagues. Emissions rose coeval with Phoenician expansion, accelerated during expanded Carthaginian and Roman mining primarily in the Iberian Peninsula, and reached a maximum under the Roman Empire. Emissions fluctuated synchronously with wars and political instability particularly during the Roman Republic, and plunged coincident with two major plagues in the second and third centuries, remaining low for >500 years. Bullion in silver coinage declined in parallel, reflecting the importance of lead-silver mining in ancient economies. Our results indicate sustained economic growth during the first two centuries of the Roman Empire, terminated by the second-century Antonine plague.

Mitochondrial Toxicity.

Recent decades have seen a rapid increase in reported toxic effects of drugs and pollutants on mitochondria. Researchers have also documented many genetic differences leading to mitochondrial diseases, currently reported to affect ∼1 person in 4,300, creating a large number of potential gene-environment interactions in mitochondrial toxicity. We briefly review this history, and then highlight cutting-edge areas of mitochondrial research including the role of mitochondrial reactive oxygen species in signaling; increased understanding of fundamental biological processes involved in mitochondrial homeostasis (DNA maintenance and mutagenesis, mitochondrial stress response pathways, fusion and fission, autophagy and biogenesis, and exocytosis); systemic effects resulting from mitochondrial stresses in specific cell types; mitochondrial involvement in immune function; the growing evidence of long-term effects of mitochondrial toxicity; mitochondrial-epigenetic cross-talk; and newer approaches to test chemicals for mitochondrial toxicity. We also discuss the potential importance of hormetic effects of mitochondrial stressors. Finally, we comment on future areas of research we consider critical for mitochondrial toxicology, including increased integration of clinical, experimental laboratory, and epidemiological (human and wildlife) studies; improved understanding of biomarkers in the human population; and incorporation of other factors that affect mitochondria, such as diet, exercise, age, and nonchemical stressors.

Organophosphorus Compounds at 80: Some Old and New Issues.

One of the major classes of pesticides is that of the organophosphates (OPs). Initial developments date back almost 2 centuries but it was only in the mid-1940s that OPs reached a prominent status as insecticides, a status that, albeit declining, is still ongoing. OPs are highly toxic to nontarget species including humans, the primary effects being an acute cholinergic toxicity (responsible for thousands of poisoning each year) and a delayed polyneuropathy. Several issues of current debate and investigation on the toxicology of OPs are discussed in this brief review. These include (1) possible additional targets of OPs, (2) OPs as developmental neurotoxicants, (3) OPs and neurodegenerative diseases, (4) OPs and the "aerotoxic syndrome," (5) OPs and the microbiome, and (6) OPs and cancer. Some of these issues have been debated and studied for some time, while others are newer, suggesting that the study of the toxicology of OPs will remain an important scientific and public health issue for years to come.

A timeline of hydrogen sulfide (H2S) research: From environmental toxin to biological mediator.

The history of H2S - as an environmental toxin - dates back to 1700, to the observations of the Italian physician Bernardino Ramazzini, whose book "De Morbis Artificum Diatriba" described the painful eye irritation and inflammation of "sewer gas" in sewer workers. The gas has subsequently been identified as hydrogen sulfide (H2S), and opened three centuries of research into the biological roles of H2S. The current article highlights the key discoveries in the field of H2S research, including (a) the toxicological studies, which characterized H2S as an environmental toxin, and identified some of its modes of action, including the inhibition of mitochondrial respiration; (b) work in the field of bacteriology, which, starting in the early 1900s, identified H2S as a bacterial product - with subsequently defined roles in the regulation of periodontal disease (oral bacterial flora), intestinal epithelial cell function (enteral bacterial flora) as well as in the regulation of bacterial resistance to antibiotics; and (c), work in diverse fields of mammalian biology, which, starting in the 1940s, identified H2S as an endogenous mammalian enzymatic product, the functions of which - among others, in the cardiovascular and nervous system - have become subjects of intensive investigation for the last decade. The current review not only enumerates the key discoveries related to H2S made over the last three centuries, but also compiles the most frequently cited papers in the field which have been published over the last decade and highlights some of the current 'hot topics' in the field of H2S biology.

Environmental Impact of Alkyl Lead(IV) Derivatives: Perspective after Their Phase-out.

The use of alkyl lead derivatives as antiknock agents in gasoline can be considered as one of the main pollution disasters of the 20th century because of both the global character of the pollution emitted and the seriousness of the impact on human health. Alkyl lead derivatives in themselves cannot be considered to be persistent pollutants because they readily degrade either before being released from the tailpipes or soon afterwards in the atmosphere. However, the inorganic lead they produced has been deposited in soils all over the planet, largely, but not exclusively in urban areas and along motorways, since the direct emission of lead into the atmosphere favored its dispersal over great distances: The signal of the massive use of alkyl lead derivatives has been found all over the world, including in remote sites such as polar areas. The short residence time of lead in the atmosphere implies that this compartment is highly responsive to changes in emissions. This was demonstrated when leaded gasoline was phased-out and is in striking contrast to the very long permanence of inorganic lead in soils, where resuspension is a permanent source of toxic lead.

Historical sediment record and levels of PCBs in sediments and mangroves of Jobos Bay, Puerto Rico.

Polychlorinated biphenyls (PCBs) were quantified in 18 surface sediment samples, 1 sediment core, and several mangrove tissue samples collected in Jobos Bay, Puerto Rico in September 2013. Total PCBs in surface sediments ranged from 0.42 to 1232ngg-1 dw. Generally, higher levels were observed near-shore close to urban and industrial areas. The levels suggest significant pollution in Jobos Bay with respect to PCBs. Two-thirds of the sites were dominated by lighter PCB congeners (tri- to penta-chlorinated PCBs) while one-third had heavy PCB congeners (hexa- to octa-chlorinated PCBs) dominant. Total PCBs in a sediment core indicated levels fluctuating according to historical usage patterns. Total PCBs were measured in mangal leaves (14-747ngg-1 dw), roots (0.26-120ngg-1 dw), and seeds (16-93ngg-1 dw), suggesting bioaccumulation from sediments. This is the first report of a historical profile of PCBs in the study area and of PCB bioaccumulation in mangroves. This article provides new and useful information on PCBs in the Caribbean area of the GRULAC region.

Historical trends of anthropogenic metals in Eastern Tibetan Plateau as reconstructed from alpine lake sediments over the last century.

Reconstructing trace metal historical trends are essential for better understanding anthropogenic impact on remote alpine ecosystems. We present results from an alpine lake sediment from the Eastern Tibetan Plateau to decipher the accumulation history of cadmium (Cd), lead (Pb) and zinc (Zn) over last century, from the preindustrial to the modern period. Cd, Pb and Zn in the sediment of Caohaizi Lake clearly suffered from atmospheric deposition, and the mining and smelting were regarded as the main anthropogenic sources. Since the mid-1990s, over 80% of trace metals were quantified from anthropogenic emissions. The temporal trends of anthropogenic metal fluxes showed that the contamination history of Pb was earlier than that of Cd and Zn, which was in agreement with the regional Pb emission history, but lagged behind the Pb decline in Europe and North America. The fluxes of anthropogenic Cd and Zn were relatively constant until the 1980s, increased sharply between the 1980s and the mid-1990s, and then kept the high values. The anthropogenic fluxes of Pb showed a marked rise around 1950, and increased sharply in the 1980s. In the mid-1990s, this flux reached the peak, and then decreased gradually. The Pb deposition flux at present in comparison with other lake records in the areas of Tibetan Plateau further demonstrated that trace metals in the Caohaizi Lake region were probably from Southwest China and South Asia. Economic development in these regions still puts pressure on the remote alpine ecosystems, and thus the impact of trace metals merits more attention.

Why Litigation-Driven History Matters: Lessons Learned from the Secret History of TCE.

Litigation drives extensive historical research but often allows only select observers to see the results. Historians have conducted untold studies for litigation that become "secret histories" because these histories are not published. An example is the historical use and regulation of the chemical trichloroethylene (TCE), a hazardous chemical at issue in much environmental litigation, but a topic virtually absent in the secondary literature. This practice seems to contravene accepted standards of open scholarship. Although not directly aligned with the traditional academic model of historical practice, however, historical research and writing for litigation achieve legitimate and important results without abandoning the discipline's professional standards. History done by consultants for litigation is neither a history of compromised standards nor as "secret" as feared.

Observational and modeling constraints on global anthropogenic enrichment of mercury.

Centuries of anthropogenic releases have resulted in a global legacy of mercury (Hg) contamination. Here we use a global model to quantify the impact of uncertainty in Hg atmospheric emissions and cycling on anthropogenic enrichment and discuss implications for future Hg levels. The plausibility of sensitivity simulations is evaluated against multiple independent lines of observation, including natural archives and direct measurements of present-day environmental Hg concentrations. It has been previously reported that pre-industrial enrichment recorded in sediment and peat disagree by more than a factor of 10. We find this difference is largely erroneous and caused by comparing peat and sediment against different reference time periods. After correcting this inconsistency, median enrichment in Hg accumulation since pre-industrial 1760 to 1880 is a factor of 4.3 for peat and 3.0 for sediment. Pre-industrial accumulation in peat and sediment is a factor of ∼ 5 greater than the precolonial era (3000 BC to 1550 AD). Model scenarios that omit atmospheric emissions of Hg from early mining are inconsistent with observational constraints on the present-day atmospheric, oceanic, and soil Hg reservoirs, as well as the magnitude of enrichment in archives. Future reductions in anthropogenic emissions will initiate a decline in atmospheric concentrations within 1 year, but stabilization of subsurface and deep ocean Hg levels requires aggressive controls. These findings are robust to the ranges of uncertainty in past emissions and Hg cycling.

Spatial distribution and historical trends of heavy metals in the sediments of petroleum producing regions of the Beibu Gulf, China.

The concentrations of As, Sb, Hg, Pb, Cd, and Ba in the surface and core sediments of the oil and gas producing region of the Beibu Gulf were measured by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Atomic Fluorescence Spectrometry (AFS), and the spatial distribution and historical trends of these elements are discussed. The results show that the concentrations of these elements are highest near the platforms. The results of Enrichment Factor (EF) and Potential Ecological Risk Index (PERI) also reveal significantly higher enrichment around the platforms, which imply that the offshore petroleum production was the cause of the unusual distribution and severe enrichment of these elements in the study area. The environment around the platforms was highly laden with toxic elements, thereby representing a very high ecological risk to the environment of the study area.

A first European scale multimedia fate modelling of BDE-209 from 1970 to 2020.

The European Variant Berkeley Trent (EVn-BETR) multimedia fugacity model is used to test the validity of previously derived emission estimates and predict environmental concentrations of the main decabromodiphenyl ether congener, BDE-209. The results are presented here and compared with measured environmental data from the literature. Future multimedia concentration trends are predicted using three emission scenarios (Low, Realistic and High) in the dynamic unsteady state mode covering the period 1970-2020. The spatial and temporal distributions of emissions are evaluated. It is predicted that BDE-209 atmospheric concentrations peaked in 2004 and will decline to negligible levels by 2025. Freshwater concentrations should have peaked in 2011, one year after the emissions peak with sediment concentrations peaking in 2013. Predicted atmospheric concentrations are in good agreement with measured data for the Realistic (best estimate of emissions) and High (worst case scenario) emission scenarios. The Low emission scenario consistently underestimates measured data. The German unilateral ban on the use of DecaBDE in the textile industry is simulated in an additional scenario, the effects of which are mainly observed within Germany with only a small effect on the surrounding areas. Overall, the EVn-BTER model predicts atmospheric concentrations reasonably well, within a factor of 5 and 1.2 for the Realistic and High emission scenarios respectively, providing partial validation for the original emission estimate. Total mean MEC:PEC shows the High emission scenario predicts the best fit between air, freshwater and sediment data. An alternative spatial distribution of emissions is tested, based on higher consumption in EBFRIP member states, resulting in improved agreement between MECs and PECs in comparison with the Uniform spatial distribution based on population density. Despite good agreement between modelled and measured point data, more long-term monitoring datasets are needed to compare predicted trends in concentration to determine the rate of change of POPs within the environment.

Historical intake and elimination of polychlorinated biphenyls and organochlorine pesticides by the Australian population reconstructed from biomonitoring data.

Quantifying the competing rates of intake and elimination of persistent organic pollutants (POPs) in the human body is necessary to understand the levels and trends of POPs at a population level. In this paper we reconstruct the historical intake and elimination of ten polychlorinated biphenyls (PCBs) and five organochlorine pesticides (OCPs) from Australian biomonitoring data by fitting a population-level pharmacokinetic (PK) model. Our analysis exploits two sets of cross-sectional biomonitoring data for PCBs and OCPs in pooled blood serum samples from the Australian population that were collected in 2003 and 2009. The modeled adult reference intakes in 1975 for PCB congeners ranged from 0.89 to 24.5ng/kgbw/day, lower than the daily intakes of OCPs ranging from 73 to 970ng/kgbw/day. Modeled intake rates are declining with half-times from 1.1 to 1.3years for PCB congeners and 0.83 to 0.97years for OCPs. The shortest modeled intrinsic human elimination half-life among the compounds studied here is 6.4years for hexachlorobenzene, and the longest is 30years for PCB-74. Our results indicate that it is feasible to reconstruct intakes and to estimate intrinsic human elimination half-lives using the population-level PK model and biomonitoring data only. Our modeled intrinsic human elimination half-lives are in good agreement with values from a similar study carried out for the population of the United Kingdom, and are generally longer than reported values from other industrialized countries in the Northern Hemisphere.

Environmental pollution and allergy: historical aspects.

It may be a coincidence, but it is a fact that the first clear characterization of hay fever began in England where modern industrialization started in Europe. Only at the end of the 20th century were associations of the increasing prevalence of allergy with outdoor air pollution discussed. The seminal study came from Japan from the group of T. Miyamoto linking the increase in Japanese cedar pollinosis to an increased prevalence of Diesel cars and probably exposure to Diesel exhaust in epidemiological, animal experimental and in vitro studies. In Germany first epidemiological studies were done in North Rhine-Westphalia and Bavaria in 1987 and 1988 showing a striking prevalence of allergic disease of up to 10-20% in preschool children. After German reunification the most surprising observation was a lower prevalence of hay fever in East German children compared to the West, although there was a much higher air pollution with SO2 and large particulate matter. Modern smog as found over West German cities most likely originating from traffic exhaust and consisting of fine and ultrafine particles was shown to be associated with higher incidence rates of allergy and allergic sensitization. In the 10 years after reunification there was a steep increase of allergy prevalence in East German children reaching almost the same level as in West Germany. Obviously, a multitude of lifestyle factors - beyond air pollution - may be involved in the explanation of this phenomenon. Surprisingly the skin manifestation of atopy, namely atopic eczema, was more frequent in East German children compared to the West, thus differing from airway allergy. Meanwhile in vitro studies and animal experiments have shown that a variety of air pollutants mostly from environmental tobacco smoke (indoors) and from traffic exhaust (outdoors) can stimulate immune cells inducing a Th2-dominated response besides their irritative effects. While 50 years ago in allergy textbooks a clear distinction was made between 'toxic' or 'allergic', the newly developed concept of allergotoxicology has stimulated research tremendously, meaning 'the investigation of effects of toxic substances upon the induction, elicitation and maintenance of allergic reactions'.

Global emission inventories for C4-C14 perfluoroalkyl carboxylic acid (PFCA) homologues from 1951 to 2030, part II: the remaining pieces of the puzzle.

We identify eleven emission sources of perfluoroalkyl carboxylic acids (PFCAs) that have not been discussed in the past. These sources can be divided into three groups: [i] PFCAs released as ingredients or impurities, e.g., historical and current use of perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA) and their derivatives; [ii] PFCAs formed as degradation products, e.g., atmospheric degradation of some hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs); and [iii] sources from which PFCAs are released as both impurities and degradation products, e.g., historical and current use of perfluorobutane sulfonyl fluoride (PBSF)- and perfluorohexane sulfonyl fluoride (PHxSF)-based products. Available information confirms that these sources were active in the past or are still active today, but due to a lack of information, it is not yet possible to quantify emissions from these sources. However, our review of the available information on these sources shows that some of the sources may have been significant in the past (e.g., the historical use of PFBA-, PFHxA-, PBSF- and PHxSF-based products), whereas others can be significant in the long-term (e.g., (bio)degradation of various side-chain fluorinated polymers where PFCA precursors are chemically bound to the backbone). In addition, we summarize critical knowledge and data gaps regarding these sources as a basis for future research.