High-temporal resolution landscape changes related to anthropogenic activities over the past millennium in the Vosges Mountains (France).

Iron mining activities in the Bruche valley (Vosges Mountains, France) date historically from the Roman period to the mid-nineteenth century. The geochemical and palynological study of a core from the peat bog of Le Champ du Feu allows highlighting impacts of these activities over the past millennium. Trace metal contamination is recorded for lead (Pb), arsenic, zinc, and antimony during the Middle Ages, the sixteenth century, and from cal. AD 1750-1900, with several sources distinguished by Pb isotope analyses. Forest exploitation is attested by the palynological analysis of the core, with exploitation of Fagus for smelting processes and cutting of Abies for agro-pastoralism. This approach highlights several patterns of contamination, corresponding to the mixing sources and the contamination intensity, which can be linked to the pollen assemblage zones. Hence, anthropogenic activities such as mining and farming led to long-term modification of the landscape composition in this mountainous area.

Assessment and review of organochlorine pesticide pollution in Kyrgyzstan.

The current study describes the preliminary assessment and securing activities of the largest and most hazardous POPs-contaminated sites in Kyrgyzstan. In 2010, cattle died and population were found with high pesticide levels in blood, human milk, and placenta. In the first phase of the study, a historic assessment of the pesticide dumping at the landfill/dump sites have been conducted. In the second phase, soil analysis for organochlorine pesticides in the areas of the pesticide disposal sites, the former pesticides storehouses, agro-air strips, and the cotton-growing fields were conducted. By this assessment, a first overview of the types and sources of pollution and of the scale of the problem is compiled including information gaps. From major pesticides used, DDT, DDE, and HCH were measured in the highest concentrations. With the limited analytical capacity present, a reasonable risk assessment could be performed. This paper also reports on practical risk reduction measures that have been carried out recently at the two major pesticide disposal sites with support of a Dutch environmental engineering company, an international NGO (Green Cross Switzerland) and local authorities from the Suzak region within an UN project. Local population living near the sites of the former pesticide storehouses and agro-airstrips are advised not to cultivate vegetables and melons or to raise cattle on these areas. Instead, it is recommended to grow technical crops or plant trees. Further recommendations on monitoring and assessment is given including the suggestion to consider the findings in the National Implementation Plan of Kyrgyzstan.

Los halos de inhibición en la remediación de suelos amazónicos contaminados con petróleo / Inhibition halos in the remediation of Amazon soils contaminated with petroleum

Resumen Se analiza la historia de la biorremediación de suelos contaminados con petróleo en la Amazonía ecuatoriana desde 1994 hasta 2014. Constatamos que si bien hubo “éxitos” tecnocientíficos, la oportunidad de cimentar un proceso de excelencia científica se vio frustrada por la carencia de voluntad política para gestionar la investigación. Parecen haber influido la dependencia de tecnología extranjera, la poca articulación interna entre programas de investigación e instituciones, la corrupción, la poca tradición innovadora en la biotecnología nacional, el predominio de biobraceros y una dicotomía construida entre petróleo y ambiente. Se articulan estos resultados en torno a debates sobre ciencia y tecnología en la periferia y se reflexiona sobre aspectos necesarios para consolidar procesos tecnocientíficos de excelencia en estos territorios.

Abstract We analyze the history of bioremediation of soils contaminated with petroleum in the Ecuadorian Amazon from 1994 to 2014. Although there were some technoscientific “successes,” we argue that the opportunity to develop a process of scientific excellence was thwarted by lack of an institutional framework and the political will to oversee research and innovation. Dependence on foreign technology, insufficient internal coordination among research programs and institutions, corruption, lack of a national tradition of biotechnological innovation, the predominance of “biopeons,” and a dichotomy between oil and the environment all influenced this process. We discuss these issues in relation to science and technology on the periphery and examine what is needed to consolidate technoscientific processes of excellence in those territories.

Inhibition halos in the remediation of Amazon soils contaminated with petroleum.

We analyze the history of bioremediation of soils contaminated with petroleum in the Ecuadorian Amazon from 1994 to 2014. Although there were some technoscientific "successes," we argue that the opportunity to develop a process of scientific excellence was thwarted by lack of an institutional framework and the political will to oversee research and innovation. Dependence on foreign technology, insufficient internal coordination among research programs and institutions, corruption, lack of a national tradition of biotechnological innovation, the predominance of "biopeons," and a dichotomy between oil and the environment all influenced this process. We discuss these issues in relation to science and technology on the periphery and examine what is needed to consolidate technoscientific processes of excellence in those territories.

Sedimentary record of PAHs in the Liangtan River and its relation to socioeconomic development of Chongqing, Southwest China.

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were detected in sediment cores and surface sediment samples from the Liangtan River of Chongqing, Southwest China. The total concentration of 16 PAHs ranged from 69 to 6251 ng g(-1). The spatial distribution of the PAHs reflects the intensity and scope of human activity in the catchment. A historical record of PAH contamination was reconstructed using a sediment core from a background segment of the river. The characteristic changes of concentrations, fluxes and patterns of 16 PAHs over the past ~90years were captured in detail. An obvious peak of PAH concentration and flux was found in the 1940s, i.e., during war time, and then a sharp increase was observed from the early 1980s to the present. The maximum concentration and flux reached 1260 ng g(-1) and 470 ng cm(-2)year(-1), respectively. The sharp increase was attributed to the contribution of pyrogenic sources of PAHs. The population, length of highways and energy consumption of Chongqing, as indexes of socioeconomic development, were positively correlated with PAH input in the sediment core from the 1950s to the present. The results clearly show that the local socioeconomic development in the last decades remarkably aggravated the environmental load of sedimentary PAHs.

Pre-industrial accumulation of anthropogenic polycyclic aromatic hydrocarbons found in a blanket bog of the Iberian Peninsula.

Studies on the temporal deposition of polycyclic aromatic hydrocarbons (PAHs) in peatlands are scarce, and none have been carried out in the Iberian Peninsula. To address this gap, ten PAHs were determined in a short peat core (spanning the last 1000 years) sampled in NW Iberian Peninsula, by HPLC-fluorescence. Fluoranthene, pyrene, benzo[b]fluoranthene and indeno[1,2,3-cd]pyrene predominated in the upper layers (10 cm), whereas fluoranthene and pyrene were the most abundant in the lower layers (40 cm), which showed an absence of high molecular weight PAHs (benzo[ghi]perylene and Indeno[1,2,3-cd]pyrene). Although increased PAH contents have been detected since 1700 A.D., coinciding with the beginning of the Metallurgical and Industrial Revolution, high levels of fluoranthene and pyrene were present in peat samples dating back to the 12th century A.D. The results suggest that changes in sources, type of emission (global or local) and transport could be responsible for the different PAH content and composition of the peat core. These changes are consistent with the history of the use of natural resources in the NW of the Iberian Peninsula.

Pyrogenic inputs of anthropogenic Pb and Hg to sediments of the Hood Canal, Washington, in the 20th century: source evidence from stable Pb isotopes and PAH signatures.

Combustion-derived PAHs and stable Pb isotopic signatures ((206)Pb/(207)Pb) in sedimentary records assisted in reconstructing the sources of atmospheric inputs of anthropogenic Pb and Hg to the Hood Canal, Washington. The sediment-focusing corrected peak fluxes of total Pb and Hg (1960-70s) demonstrate that the watershed of Hood Canal has received greater atmospheric inputs of these metals than its mostly rural land use would predict. The tight relationships between the Pb, Hg, and organic markers in the cores indicate that these metals are derived from industrial combustion emissions. Multiple lines of evidence point to the Asarco smelter, located in the Main Basin of Puget Sound, as the major emission source of these metals to the watershed of the Hood Canal. The evidence includes (1) similar PAH isomer ratios in sediment cores from the two basins, (2) the correlations between Pb, Hg, and Cu in sediments and previously studied environmental samples including particulate matter emitted from the Asarco smelter's main stack at the peak of production, and (3) Pb isotope ratios. The natural rate of recovery in Hood Canal since the 1970s, back to preindustrial metal concentrations, was linear and contrasts with recovery rates reported for the Main Basin which slowed post late 1980s.

Using a two site-reactive model for simulating one century changes of Zn and Pb concentration profiles in soils affected by metallurgical fallout.

Predicting the transfer of contaminants in soils is often hampered by lacking validation of mathematical models. Here, we applied Hydrus-2D software to three agricultural soils for simulating the 1900-2005 changes of zinc and lead concentration profiles derived from industrial atmospheric deposition, to validate the tested models with plausible assumptions on past metal inputs to reach the 2005 situation. The models were set with data from previous studies on the geochemical background, estimated temporal metal deposition, and the 2005 metal distributions. Different hypotheses of chemical reactions of metals with the soil solution were examined: 100% equilibrium or partial equilibrium, parameterized following kinetic chemical extractions. Finally, a two-site model with kinetic constant values adjusted at 1% of EDTA extraction parameters satisfactory predicted changes in metal concentration profiles for two arable soils. For a grassland soil however, this model showed limited applicability by ignoring the role of earthworm activity in metal incorporation.

Reconstructing historical trends of Berre lagoon contamination from surface sediment datasets: influences of industrial regulations and anthropogenic silt inputs.

These last decades, the Berre lagoon (in southeastern France) has been deeply affected since the 1930s by strong inputs of contaminants associated with industrial development and since 1966 by huge inputs of freshwater and silts due to the installation of a hydroelectric power plant. Surveys of the surface sediment contamination have been sparsely performed since 1964 for management and research purposes. These surveys were performed by various laboratories that investigated different chemicals and sampling areas using different analysis protocols. Therefore, the available data are disconnected in time and space and differ in quality. In order to reconstruct coherent time series of sediment contamination from this heterogeneous datasets and to discuss the influences of industrial and hydroelectric discharges we used a statistical approach. This approach is based on Principal Component Analysis (PCA) and Fuzzy clustering analysis on data from one extensive survey realized on surface sediments in 1976. The PCA allowed identifying two geochemical indexes describing the main surface sediment geochemical characteristics. The fuzzy clustering analysis on these indexes allowed identifying sub-areas under the specific influence of industrial or hydroelectric discharges. This allowed us to reconstruct, for each sub-area, a coherent and interpretable long-term time series of sediment contamination from the available database. Reconstructed temporal trends allowed us to estimate: (i) the overall decrease of sediment contamination since the mid-1970 attributed to industrial discharge regulations enacted at this period and (ii) the dilution of the concentrations of sediment bound contaminants induced by the hydroelectric power plant and its associated particulate matter inputs.

Breaking sod or breaking even? Flax on the northern Great Plains and Prairies, 1889-1930.

A new thirst for paint and color in cities made extensive flax production profitable in the northern Great Plains and Prairies and contributed to the cultivation of the most fragile grassland ecosystems. The production of flax seed for linseed oil became an early spin-off of the Prairie wheat economy but, unlike wheat, flax vanished from old land after one or two rotations and reappeared in districts with the most new breaking. Officials explained the migrant crop as preparing native grasslands for cultivation or exhausting soil in old land, but farmers brought flax to their new breaking for other reasons. Producers would only put flax on any land when a range of economic and environmental conditions were in place. It was never sown without promise of adequately high prices or in the absence of affordable seed and other inputs. When price allowed, it usually appeared on new breaking because it could be planted later and transported further without upsetting the balance of other activities and without farmers learning many new techniques. Scientists discovered that diseased soil drove flax off old land, not soil exhaustion. Circumventing the disease was possible but costly, and farmers simply replaced flax with the next most lucrative commodity.

Modelling historical budget of alpha-hexachlorocyclohexane in Taihu Lake, China.

Historical alpha-hexachlorocyclohexane (alpha-HCH) budget in Taihu Lake (TL), China has been simulated by a Gridded Basin-based Pesticide Mass Balance Model (GB-PMBM). Using annual usage of alpha-HCH from 1952 to 1984 as input, the model outputs included annual concentrations in air, water and sediment in TL, and annual cumulative burden of alpha-HCH in the lake water and sediment from 1952 to 2008. Model results showed that the modeled alpha-HCH in the air, water and sediment matched their corresponding measured data well, and the current levels of alpha-HCH in the air, water and sediment in TL in 2008 are 11.7 (3.4-22.7) pgm(-3), 0.8 (0.3-1.5) ng L(-1) and 0.18 (0.04-0.46) ng g(-1)dw (dry weight), respectively. The alpha-HCH burden in TL water started to accumulate after 1952, reached the highest value of 11,000kg in 1972, decreased very quickly since the beginning of 1980s, reduced to 200 kg in 1984 and 3 kg in 2008. It was found that TL water played a role of "distributor" in process of transport of alpha-HCH. Before 1980, TL water took a large amount of alpha-HCH from atmosphere through a huge air-water interface and carried a major portion of it out of the lake through water current. After 1980, TL water took alpha-HCH from lake sediments and river water entering the lake, and released almost all of it to air. The lake water itself cannot hold a large portion of the chemical due to its shallow depth and short residence time.

Historical record of black carbon in urban soils and its environmental implications.

Energy use in urbanization has fundamentally changed the pattern and fluxes of carbon cycling, which has global and local environmental impacts. Here we have investigated organic carbon (OC) and black carbon (BC) in six soil profiles from two contrast zones in an ancient city (Nanjing) in China. BC in soils was widely variable, from 0.22 to 32.19 g kg(-1). Its average concentration in an ancient residential area (Zone 1) was, 0.91 g kg(-1), whereas in Zone 2, an industrial and commercial area, the figure was 8.62 g kg(-1). The ratio of BC/OC ranged from 0.06 to 1.29 in soil profiles, with an average of 0.29. The vertical distribution of BC in soil is suggested to reflect the history of BC formation from burning of biomass and/or fossil fuel. BC in the surface layer of soils was mainly from traffic emission (especially from diesel vehicles). In contrast, in cultural layers BC was formed from historical coal use. The contents of BC and the ratio of BC/OC may reflect different human activities and pollution sources in the contrasting urban zones. In addition, the significant correlation of heavy metals (Cu, Pb, and Zn) with BC contents in some culture layers suggests the sorption of the metals by BC or their coexistence resulted from the coal-involved smelting.

Historical PCB fluxes in the Mexico City Metropolitan Zone as evidenced by a sedimentary record from the Espejo de los Lirios lake.

The accumulation of PCBs over time was studied in a sediment core collected from Espejo de los Lirios, an ecological reserve located within the heart of Cuatitlan Izcalli, in the Northern part of Mexico City Metropolitan Zone. A (210)Pb-derived chronology, was used to reconstruct the historical PCB fluxes to the site during approximately 84 yr (1911-95). The highest input fluxes occurred in the 1977, after a significant increase after the late 1940s. This trend is clearly the consequence of the increasing emissions that are related to the onset of industrial activities starting from early 1970s. A phase of decrease, after the ban of the use in open systems, ended in 1989 and in 1995, at the time of sampling, the trend was toward a new increase to the highest levels. A reconstruction of PCB atmospheric concentration from sedimentary fluxes is attempted; and the estimate suggests that PCBs concentrations in the air of the Cuautitlán Izcalli seem not of concern. Nonetheless, the contamination levels found in the sediments are relatively high, reaching values above the threshold effect level (TEL) guidelines and, in two cases, close to the probable effect level (PEL) which mean that some adverse effects on the fauna may have occurred all over the time interval represented by the core.

Historical changes in the concentrations of selenium in soil and wheat grain from the Broadbalk experiment over the last 160 years.

Selenium (Se) intake has decreased substantially in the UK population since 1970s. To investigate whether Se concentration in wheat grain has changed as a result of yield improvement or environmental changes, we analyzed archived wheat grain from the Broadbalk Wheat Experiment at Rothamsted, England, which has been run continuously for over 160 years. Wheat grain and soil samples were selected from plots receiving different fertilizer or manure treatments. Grain Se concentration varied from 11 to 236 ng g(-1), with a mean and median of 44 and 32 ng g(-1), respectively. Grain samples from the unfertilized control plot had significantly higher concentrations of Se than those from fertilized or manured plots; the latter received various amounts of S and also had higher grain yield. No significant trends in grain Se concentrations were detected in the fertilized or manured plots, in spite of a dramatic increase in grain yield since the introduction of modern short-straw cultivars in the mid 1960s. In the control plot, grain samples had higher Se concentrations in the periods before 1920 or after 1970 than those during 1920-1970. This temporal pattern mirrored that of SO(2) emissions and atmospheric S deposition. Soil Se concentrations showed an increasing trend in all plots over 160 years. The results show that the Se concentration of wheat grain from the Broadbalk experiment was influenced by S inputs from fertilizers and atmospheric deposition, and that improving grain yield through plant breeding has not resulted in a significant decrease in grain Se concentration in the fertilized plots.

Lead fluxes, isotopic and concentration profiles in a peat deposit near a lead smelter (Príbram, Czech Republic).

The content and the isotopic composition of lead (Pb) were studied in a peat deposit on the ridge of the Brdy Hills, in the vicinity of the Príbram metallurgical works, in the Czech Republic. Quadrupole ICP MS was employed to determine the elemental composition and (206)Pb/(207)Pb and (208)Pb/(206)Pb isotope ratios. The individual layers were dated using alpha spectrometric measurement of the (210)Pb activity. The historical time period covered by the studied cores reached back to the 18th century. The Pb concentration in the studied profiles varied from 10 to 550 mg kg(-1). The (206)Pb/(207)Pb ratio varied in the range from 1.154 to 1.194 in the individual parts of the profile. The metallurgy of the Pb ores ((206)Pb/(207)Pb approximately 1.16), lithogenic Pb ((206)Pb/(207)Pb approximately 1.2), metallurgical processing of automobile batteries ((206)Pb/(207)Pb approximately 1.17) and the combustion of coal ((206)Pb/(207)Pb approximately 1.17-1.19) yield isotopic signatures that determine the isotope compositions of the individual profiles. Deposition rates between 15 mg m(-2) year(-1) at the beginning of the 19th century and 320 mg m(-2) year(-1) in the 1980s were determined in the dated profiles. The increased deposition rates determined on the dated profiles correspond to the increasing production of Pb ores in the Príbram mining area at the turn of the 19th and 20th centuries. The maximum for metallurgical production corresponds to the highest deposition rates recorded in 1960s and 1970s. The current deposition rate of 5-89 mg m(-2) year(-1) Pb is related to erosion of contaminated soils and waste dumps.

A comparison of antimony and lead profiles over the past 2500 years in Flanders Moss ombrotrophic peat bog, Scotland.

Two cores collected in 2001 and 2004 from Flanders Moss ombrotrophic peat bog in central Scotland were dated (14C, 210Pb) and analysed (ICP-OES, ICP-MS) to derive and compare the historical atmospheric deposition records of Sb and Pb over the past 2500 years. After correction, via Sc, for contributions from soil dust, depositional fluxes of Sb and Pb peaked from ca. 1920-1960 A.D., with >95% of the anthropogenic inventories deposited post-1800 A.D. Over the past two centuries, trends in Sb and Pb deposition have been broadly similar, with fluctuations in the anthropogenic Sb/Pb ratio reflecting temporal variations in the relative input from emission sources such as the mining and smelting of Pb ores (in which Sb is commonly present, as at Leadhills/Wanlockhead in southern Scotland), combustion of coal (for which the Sb/Pb ratio is approximately an order of magnitude greater than in Pb ores) and exhaust emissions (Pb from leaded petrol) and abrasion products from the brake linings (Sb from heat-resistant Sb compounds) of automobiles. The influence of leaded petrol has been most noticeable in recent decades, firstly through the resultant minima in Sb/Pb and 206Pb/207Pb ratios (the latter arising from the use of less radiogenic Australian Pb in alkylPb additives) and then, during its phasing out and the adoption of unleaded petrol, complete by 2000 A.D., the subsequent increase in both Sb/Pb and 206Pb/207Pb ratios. The extent of the 20th century maximum anthropogenic enrichment of Sb and Pb, relative to the natural Sc-normalised levels of the Upper Continental Crust, was similar at approximately 50- to 100-fold. Prior to 1800 A.D., the influence of metallurgical activities on Sb and Pb concentrations in the peat cores during both the Mediaeval and Roman/pre-Roman periods was discernible, small Sb and Pb peaks during the latter appearing attributable, on the basis of Pb isotopic composition, to the mining/smelting of Pb ores indigenous to Britain.

Historical change of heavy metals in urban soils of Nanjing, China during the past 20 centuries.

Two typical areas, including once commercial and residential quarters of Nanjing, China, were studied by investigating soil properties especially heavy metals of soils in various cultural layers formed in different Chinese Dynasties. The age of the soil profiles was dated by both archaeological and 14C chronological methods. The results showed that urban soils in the old commercial/workshop quarter of Nanjing were generally contaminated by heavy metals Cu, Zn, Pb, but their concentration levels varied significantly among the cultural layers formed in different dynasties. The substantial increase of heavy metals appeared in three historical periods, i.e., South Dynasty (222-589 AD), the earlier Ming (1368-1644 AD) and the late Qing (1644-1912 AD) in one area. The tremendous input and storage of heavy metals in soils was explained by the primitive smelting and the strengthened metal processing activities, which might be due to the requirement of weapon making or other industries, in the changing social conditions of the corresponding periods. Soils in the once noble political, cultural centers did not show significant increase of heavy metals. The difference in the distribution pattern of heavy metals revealed the contrasting history of the site uses. The change of contaminant level in soils is believed to be a reflection of various human activities in the city during the past 20 centuries.

Natural mercury enrichment in a minerogenic fen--evaluation of sources and processes.

Mercury (Hg) records in natural archives such as peat bogs are often used to evaluate anthropogenic or climatic influences on atmospheric Hg deposition. In this context, there is an ongoing discussion about natural sources or processes of Hg enrichment in natural archives. In the present study we estimated Hg fluxes from rock weathering, direct atmospheric deposition and from indirect atmospheric deposition in the catchment of a pristine minerogenic fen (GC2) located in the Magellanic Moorlands, southernmost Chile. The Hg record in the bog covers 11 174 cal. (14)C years and shows Hg concentrations of up to 570 [micro sign]g kg(-1) with an average of 268 [micro sign]g kg(-1). Hg was found to be enriched in the peat by a factor of 81 if compared to the mean Hg concentrations in the rocks of the catchment (3.2 [micro sign]g kg(-1)). Hg and also Pb, Fe, and As were found to be enriched predominately in goethite layers indicating high retention of these elements in the bog by iron oxyhydrates. It could also be demonstrated that the high peat decomposition rates in minerogenic bogs can increase the Hg concentrations in the minerogenic peat by a factor of approximately 2 at the same atmospheric Hg deposition rate if compared to ombrotrophic sites. This study has shown that Hg in minerogenic peat can be naturally enriched especially through the retention by autochthonous formed goethite and can be a solely internal process which does not require increased external Hg fluxes.

Observations on historical, contemporary, and natural PCDD/Fs.

PCDD/Fs were determined in samples of archived surface soils collected from different locations around the world in the early 1880s, in contemporary surface soils from around the world, in archived subsurface soils collected at Rothamsted Experimental Station in the 1870/1880s, and in sections of peat core deposited between 5000 BP and the present. PCDD/Fs were detected in most of the samples. The potential sources and implications of the levels and mixtures of PCDD/Fs present in the samples are discussed. The homologue and isomer patterns observed in most of the contemporary European surface soils are commonly observed for European air samples and soil samples. The homologue pattern in the Rothamsted surface soils collected in the 1800s was similar, suggesting that similar sources of atmospheric emissions of PCDD/ Fs were operating in the UK in the 1800s as currently. Very different patterns, dominated by OCDD and with contributions of HpCDD and HxCDD, were found in some other samples. It is proposed that the PCDD/Fs present in the subsurface Rothamsted soils, archived (1880s) surface soils from Illinois and the Congo, clay beneath the peat bog (deposited approximately 5000 BP), and possibly surface soil samples from Thailand and Australia are of a natural origin. The most abundant TeCDD/F congeners measured in the peat samples here were also those observed by previous workers who studied a Canadian peat bog and are consistent with the microbially mediated oxidative coupling of chlorophenols. The study provides evidence for the widespread occurrence of PCDD/Fs in the environment prior to 1900 and for a complex array of sources (including natural) and environmental transformation processes.