A comparative study of As(III) and As(V) in aqueous solutions and adsorbed on iron oxy-hydroxides by Raman spectroscopy

The sorption of the arsenite (AsO₃³⁻) and the arsenate (AsO₄³⁻) ions and their conjugate acids onto iron oxides is one of main processes controlling the distribution of arsenic in the environment. The present work intends to provide a large vibrational spectroscopic database for comparison of As(III) and As(V) speciation in aqueous solutions and at the iron oxide - solution interface. With this purpose, ferrihydrite, feroxyhyte, goethite and hematite were firstly synthesized, characterized in detail and used for adsorption experiments. Raman spectra were recorded from As(III) and As(V) aqueous solutions at various pH conditions selected in order to highlight arsenic speciation. Raman Scattering and Diffuse Reflectance Infrared Fourier Transform (DRIFT) studies were carried out to examine the respective As-bonding mechanisms. The collected data were curve-fitted and discussed according to molecular symmetry concepts. X-ray Absorption Near Edge Spectroscopy (XANES) was applied to confirm the oxidation state of the sorbed species. The comprehensive spectroscopic investigation contributes to a better understanding of arsenic complexation by iron oxides.     

Mercury and methylmercury concentrations in high altitude lakes and fish (Arctic charr) from the French Alps related to watershed characteristics

Total mercury (THg) and methylmercury (MeHg) concentrations were measured in the muscle of Arctic charr (Salvelinus alpinus) and in the water column of 4 lakes that are located in the French Alps. Watershed characteristics were determined (6 coverage classes) for each lake in order to evaluate the influence of watershed composition on mercury and methylmercury concentrations in fish muscle and in the water column. THg and MeHg concentrations in surface water were relatively low and similar among lakes and watershed characteristics play a major role in determining water column Hg and MeHg levels. THg muscle concentrations for fish with either a standardized length of 220 mm, a standardized age of 5 years or for individualuals did not exceed the 0.5 mg kg^− 1 fish consumption advisory limit established for Hg by the World Health Organization (WHO, 1990). These relatively low THg concentrations can be explained by watershed characteristics, which lead to short Hg residence time in the water column, and also by the short trophic chain that is characteristic of mountain lakes. Growth rate did not seem to influence THg concentrations in fish muscles of these lakes and we observed no relationship between fish Hg concentrations and altitude. This study shows that in the French Alps, high altitude lakes have relatively low THg and MeHg concentrations in both the water column and in Arctic charr populations. Therefore, Hg does not appear to present a danger for local populations and the fishermen of these lakes.     

Potential nitrate removal in a coastal freshwater sediment (Haringvliet Lake, The Netherlands) and response to salinization

Nitrogen transformations and their response to salinization were studied in bottom sediment of a coastal freshwater lake (Haringvliet Lake, The Netherlands). The lake was formed as the result of a river impoundment along the south-western coast of the Netherlands, and is currently targeted for restoration of estuarine conditions. Nitrate porewater profiles indicate complete removal of NO(3)(-) within the upper few millimeters of sediment. Rapid NO(3)(-) consumption is consistent with the high potential rates of nitrate reduction (up to 200 nmol N cm(-3) h(-1)) measured with flow-through reactors (FTRs) on intact sediment slices. Acetylene-block FTR experiments indicate that complete denitrification accounts for approximately half of the nitrate reducing activity. The remaining NO(3)(-) reduction is due to incomplete denitrification and alternative reaction pathways, most likely dissimilatory nitrate reduction to NH(4)(+) (DNRA). Results of FTR experiments further indicate that increasing bottom water salinity may lead to a transient release of NH(4)(+) and dissolved organic carbon from the sediment, and enhance the rates of nitrate reduction and nitrite production. Increased salinity may thus, at least temporarily, increase the efflux of NH(4)(+) from the sediment to the surface water. This work shows that salinity affects the relative importance of denitrification compared to alternative nitrate reduction pathways, limiting the ability of denitrification to remove bioavailable nitrogen from aquatic ecosystems.     

Amazonian former gold mined soils as a source of methylmercury: evidence from a small scale watershed in French Guiana

Total mercury (HgT) and monomethylmercury (MMHg) were investigated in a tropical head watershed (1 km²) of French Guiana. The watershed includes a pristine area on the hill slopes and a former gold mined flat in the bottomland. Concentrations of dissolved and particulate HgT and MMHg were measured in rain, throughfall, soil water and at three points along the stream. Samples were taken in-between and during 14 storm events at the beginning and middle of the 2005 and 2006 rainy seasons. Dissolved and particulate HgT concentrations in the stream slightly increased downstream, while dissolved and particulate MMHg concentrations were low at the pristine sub-watershed outlet (median = 0.006 ng L⁻¹ and 1.84 ng g⁻¹, respectively) and sharply increased at the gold mined flat outlet (median = 0.056 ng L⁻¹ and 6.80 ng g⁻¹, respectively). Oxisols, which are dominant in the pristine area act as a sink of HgT and MMHg from rain and throughfall inputs. Hydromorphic soils in the flat are strongly contaminated with Hg (including Hg⁰ droplets) and their structure has been disturbed by former gold-mining processes, leading to multiple stagnant water areas where biogeochemical conditions are favorable for methylation. In the former gold mined flat high dissolved MMHg concentrations (up to 0.8 ng L⁻¹) were measured in puddles or suboxic soil pore waters, whereas high dissolved HgT concentrations were found in lower Eh conditions. Iron-reducing bacteria were suggested as the main methylators since highest concentrations for dissolved MMHg were associated with high dissolved ferrous iron concentrations. The connection between saturated areas and stagnant waters with the hydrographic network during rain events leads to the export of dissolved MMHg and HgT in stream waters, especially at the beginning of the rainy season. As both legal and illegal gold-mining continues to expand in French Guiana, an increase in dissolved and particulate MMHg emissions in the hydrographic network is expected. This will enhance MMHg bio-amplification and present a threat to local populations, whose diet relies mainly on fish.     

Effects of submerged macrophytes on sediment resuspension and internal phosphorus loading in Lake Hiidenvesi (southern Finland)

The effects of submerged macrophytes on sediment resuspension and internal phosphorus loading in the shallow Kirkkoj?rvi basin of Lake Hiidenvesi were studied by sedimentation traps and sediment and water samples. During the 83 d study period, 793 g DW m(-2) of sediment was resuspended within the stand formed by Ranunculus circinatus, Ceratophyllum demersum and Potamogeton obtusifolius. Outside the stand, 1701g DW m(-2) sediment resuspension was measured during the same period. Water turbidity and concentration of suspended solids (SS) were significantly lower within the plant bed compared with the surrounding water area. Despite the higher concentration of inorganic suspendoids, the concentration of chlorophyll a was higher in the open water than within the submerged plant bed, owing to the enhanced nutrient recycling rate in the absence of submerged plants. With the resuspended sediment, 11.8 mg Pm(-2)d(-1) was brought into the water column within the stand and 24.5 mg Pm(-2)d(-1) outside the stand. Within the macrophyte stand, resuspended particles absorbed phosphorus from the water (indicated by the inverse relationship between SS and soluble reactive phosphorus), which was probably connected to the lowered phosphorus concentration of surface sediment due to uptake by macrophytes.     

Building materials as intrinsic sources of sulphate: a hidden face of salt weathering of historical monuments investigated through multi-isotope tracing (B, O, S)

Sulphate neoformation is a major factor of degradation of stone monuments. Boron, sulphur and oxygen isotope signatures were investigated for five French historical monuments (Bourges, Chartres and Marseille cathedrals, Chenonceau castle, and Versailles garden statues) to investigate the role of intrinsic sulphate sources (gypsum plasters and mortars) in stone degradation, compared to the influence of extrinsic sources such as atmospheric pollution. Gypsum plasters and gypsum-containing mortars fall systematically in the δ³⁴S and δ¹⁸O range of Paris Basin Eocene evaporites indicating the origin of the raw materials (so-called "Paris plaster"). Black crusts show the typical S and O isotope signatures observed elsewhere in Europe that can be attributed to atmospheric pollution, together with a marine component for Marseille. Boron isotopes for black crusts indicate coal combustion as principal boron source. Mortar isotope compositions discriminate three types, one similar to gypsum plasters, one strongly depleted in ³⁴S, attributed to pyrite oxidation, and a third one close to atmospheric sulphates. The isotopic composition of sulphates and boron of most degraded building stones of the different monuments is well explained by the identified sulphate sources. In several cases (in particular for Chenonceau and Bourges, to some extent for Chartres), the impact of gypsum plaster as building and restoration material on the degradation of the stones in its vicinity was clearly demonstrated. The study illustrates the usefulness of multi-isotope studies to investigate stone degradation factors, as the combination of several isotope systematics increases the discriminatory power of isotope studies with respect to contaminant sources.     

Particle‐associated polycyclic aromatic hydrocarbons in a representative urban location (indoor‐outdoor) from South Europe: Assessment of potential sources and cancer risk to humans

PM₁₀‐bound polycyclic aromatic hydrocarbons (PAHs) levels were monitored at urban locations (outdoor/indoor) within the city of Madrid between May 2017 and April 2018. Fourteen PAH congeners were measured, potential emission sources were identified as were potential carcinogenic risks. The ΣPAHs averaged 0.577 and 0.186 ng/m³ in outdoor and indoor air, with a high linear correlation per individual mean PAH and month. The largest contributors to the ΣPAHs were the high‐molecular‐weight PAHs. Principal component analysis‐multiple linear regression results showed that emissions from diesel and vehicular processes explained 27% and 23% of the total variance of outdoor and indoor air, while combustion processes accounted for 30% and 25% in ambient and indoor air, respectively. During the cold season, biomass burning plus coal and wood combustion were additional sources of outdoor emissions. The heavy‐, medium‐ and light‐molecular‐weight PAH originating from outdoor sources accounted for 72%, 80%, and ~60% of the indoor levels of the three respective PAH groups. Average BaP concentration was 0.029 and 0.016 ng/m³ in outdoor and indoor air, respectively. Estimated BaPeq concentration averaged 0.072, 0.035, and 0.027 ng/m³ for outdoor, indoor, and indoor‐generated individual PAH concentrations, respectively. The estimated carcinogenic risk falls within the range of acceptable risk targeted by the US‐EPA.     

The effect of a wildfire on stream water quality and catchment water yield in a tropical savanna excluded from fire for 10 years (Kakadu National Park, North Australia)

The wet/dry tropics of the Australian savannas are particularly prone to fire due to the highly seasonal rainfall and accumulation of grassy fuels. The effect of an early dry season wildfire (May, 1998) on the water quality of a seasonally flowing stream (December-June) was examined for a lowland savanna forest in Kakadu National Park (northern Australia) which had remained unburnt for 10 years. The water quality variables assessed were: total and volatile suspended sediment, phosphorus, nitrogen, iron and manganese. Compared to three years of pre-fire water quality data and 5 years of stream flow data, there was no detectable impact of the wildfire on the volume of stream flow, mean concentrations and the total mass transported by the stream for each water quality variable, except possibly nitrogen. The limited effect on water quality is attributed primarily to the timing of the wildfire and the low intensity relative to fires later in the dry season (September). The retention of canopy cover and the accumulation of leaf litter following the wildfire, and the catchment's gently undulating terrain all contributed to the negligible impact on water quality. Early dry season fires appear to be a viable management option for reducing accumulated fuel loads and hence reducing the risk of destructive wildfires later in the dry season.     

The accumulation levels of PAHs, PCBs and DDTs are related in an inverse way to the size of a benthic amphipod (Echinogammarus stammeri Karaman) in the River Po

The accumulation of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and DDTs were investigated in gammarids captured at three sites along the middle River Po; the first was located upstream and the other two were at increasing distances downstream of the confluence of a polluted tributary, the River Lambro. Using a GC-MS technique, the levels of PCBs, PAHs and DDTs were determined separately in large and small gammarids as well as in the fine fraction of sediment samples collected along the sites of capture. Results confirm the River Lambro as a source of these chemicals to the River Po, and show that bioaccumulation differences exist between small and large individuals, the former being more contaminated particularly by PCBs and DDTs. This is likely the result of several interacting factors such as contaminant bioavailability, gammarid-size effects on kinetic parameters and feeding selectivity. The bioaccumulation patterns of PCBs and DDTs, and their higher biota-sediment accumulation factors (BSAF), are consistent with chemical properties and suggest a dietary disequilibrium found only 10 km downstream from the tributary, and in smaller amphipods. Present results show that gammarids may represent an additional source of contaminants, particularly of chlorinated compounds, to the many organisms feeding on them, with a higher risk for those which prey selectively on smaller gammarids.     

Spatial and temporal trends of volatile organic compounds (VOC) in a rural area of northern Spain

Ambient concentrations of volatile organic compounds (VOCs) were measured at 40 rural sampling points in Navarre (northern Spain). Air samples were collected by means of sorbent passive sampling and analyzed by thermal desorption (TD) and gas chromatography/mass-selective detector (GC/MSD). A total of 140 VOCs were identified during the study, which was carried out between May to October 2004 for a total of a 10 biweekly sampling campaigns. Concentrations of benzene, toluene, ethylbenzene, m/p-xylenes, o-xylene (BTEX) and 1,3,5-trimethylbenzene were determined in order to investigate their temporal and spatial distributions. Geostatistical analysis pointed to traffic as the main emission source of these compounds. Supporting this idea, BTEX and nitrogen oxides concentrations were found to be highly significantly correlated (r = 0.495, P = 0.001), whereas a strong negative correlation between BTEX and ozone was also observed (r = -0.355, P = 0.025). The concentrations for the BTEX group were similar to the values that have been previously reported for other rural areas.     

Dynamic behavior of indoor ultrafine particles (2.3‐64 nm) due to burning candles in a residence

A major source of human exposure to ultrafine particles is candle use. Candles produce ultrafine particles in the size range under 10 nm, with perhaps half of the particles less than 5 nm. For these small particles at typically high concentrations, coagulation and deposition are two dominant mechanisms in aerosol size dynamics. We present an updated coagulation model capable of characterizing the relative contributions of coagulation, deposition, and air exchange rates. Size‐resolved coagulation and decay rates are estimated for three types of candles. Number, area, and mass distributions are provided for 93 particle sizes from 2.33 to 64 nm. Total particle production was in the range of 10¹³ min^?1. Peak number, area, and mass concentrations occurred at particle sizes of <3, 20, and 40 nm, respectively. Both the number and area concentrations greatly exceeded background concentrations in the residence studied. Contributions of coagulation, deposition, and air exchange rates to particle losses were 65%, 34%, and 0.3% at high concentrations (10⁶ cm^?3), while they are 17%, 81%, and 1.7% at lower concentrations (3 × 10⁴ cm^?3), respectively. The increased particle production for the very smallest particles (2.33‐2.50 nm) suggests that even smaller particles may be important to study.     

Evaluation of distribution, mobility and binding behaviour of heavy metals in surficial sediments of Louro River (Galicia, Spain) using chemometric analysis: a case study

Contents of total and extractable heavy metals, carbonates, MnO and Fe₂O₃, organic matter, and matrix components such as SiO₂, Al₂O₃, CaO, Na₂O, MgO, TiO₂, K₂O and P₂O₅ are used along with principal component analysis (PCA) for studying distribution, mobility and binding behaviour of Cd, Cr, Cu, Ni and Pb in the Louro River (Galicia, Spain). Eleven surficial sediment samples were taken along the beds of the river course. Total metal concentrations were obtained after microwave-assisted digestion whilst extractable metal contents were obtained following a three-stage sequential extraction scheme (i.e. soluble, reducible and oxidisable fractions). Loading plots of heavy metals bound to carbonates, Fe–Mn oxides, organic matter and aluminosilicates allowed determination of binding behaviour. Correlations found indicate that Pb and Cu are mainly discharged from urban wastes, whereas Cr and Ni are from electroplating and galvanizing industries. The occurrence of diffuse pollution sources along the river can account for the binding behaviour of Cd. Metal mobility decreased in the order: Cd>Pb>Cu>Ni>Cr. Despite total contents indicating moderate-to-high heavy metal pollution in this river, metals are mostly distributed in the residual fraction, hence showing a low risk of mobility.     

The application of a recently isolated strain of Bacteroides (GB-124) to identify human sources of faecal pollution in a temperate river catchment

Recent work has suggested that bacteriophages infecting Bacteroides are a potential tool for faecal source tracking, but that different host strains may be needed for different geographic areas. This study used a recently identified strain of Bacteroides (GB-124) to detect human sources of faecal pollution in a river catchment in southeast England (UK). A total of 306 river water, municipal wastewater and animal samples were obtained over a 16-month period. Bacteriophages capable of infecting GB-124 were present in all municipal wastewaters but were not detected in faecal samples from animals, and were detected at significantly lower levels (P< 0.001) in river waters directly downstream of a dairy farm. This last observation was despite the presence of high levels of faecal indicator bacteria at this site. The study suggests that GB-124 appears to be specific to human faeces. As such it may represent an effective and low-cost method of faecal source identification.     

A multi-scale analysis of urban form and commuting change in a small metropolitan area (1990–2000)

Issues of growth, especially the spatial nature of recent urban development and its implications for travel patterns, have received a great deal of attention. In particular, questions persist as to how the spatial distribution of workers and jobs influences commute patterns. This paper investigates changes in commuting and land use patterns using measures of jobs–housing balance, commuting efficiency and other statistics. A smaller urban area is chosen for study (Tallahassee, FL, USA)and data on its workers, jobs, and commute patterns are obtained from the Census Transportation Planning Package for 1990 and 2000. The key research questions investigated probe whether there were substantial changes in urban form and commuting over the period. A two-tiered approach is taken where change is explored at the regional and local scales using GIS, optimization procedures, and inferential statistical techniques. The results reveal the extent of the spatial changes in the study area between 1990 and 2000. Major findings included stability in urban structure over the time period, as well as a persistent strong relationship between land use and commute patterns. These results are discussed in light of their implications for other cities and for future work.     

Spread or backwash: The impact on population dynamics and business performance of a new road in a rural county of Galicia (Spain)

The natural experiment provided by the opening of a section that completed the A8 motorway in Mariña de Lugo, a rural area in Galicia (Spain), offers an opportunity to identify whether spread or backwash effects in economic activity are observed. The new section directly affects only a small strip of the territory—where the transition from the inland rural areas to the more dynamic coastal area takes place. This allows us to test a separate dual inner-coastal socio-economic performance after the opening of the new road—an analysis that has rarely been performed for rural areas in developed countries. We study the impact over population growth, employment and business financial results, using the differences-in-differences approach. The results we obtain are consistent with the spread hypothesis for the nearest municipality to the new road section, while the spread effects did not disseminate to the neighbouring municipalities. These global results hide a different performance at the sector level, positive for transport and manufacturing companies, and negative for retail firms and hospitality.     

Characterizations,relationship, and potential sources of outdoor and indoor particulate matter bound polycyclic aromatic hydrocarbons (PAHs) in a community of Tianjin,Northern China

Polycyclic aromatic hydrocarbons (PAHs) are among the most toxic air pollutants in China. However, because there are unsubstantial data on indoor and outdoor particulate PAHs, efforts in assessing inhalation exposure and cancer risk to PAHs are limited in China. This study measured 12 individual PAHs in indoor and outdoor environments at 36 homes during the non‐heating period and heating period in 2009. Indoor PAH concentrations were comparable with outdoor environments in the non‐heating period, but were lower in the heating period. The average indoor/outdoor ratios in both sampling periods were lower than 1, while the ratios in the non‐heating period were higher than those in the heating period. Correlation analysis and coefficient of divergence also verified the difference between indoor and outdoor PAHs, which could be caused by high ventilation in the non‐heating period. To support this conclusion, linear and robust regressions were used to estimate the infiltration factor to compare outdoor PAHs to indoor PAHs. The calculated infiltration factors obtained by the two models were similar in the non‐heating period but varied greatly in the heating period, which may have been caused by the influence of ventilation. Potential sources were distinguished using a diagnostic ratio and a mixture of coal combustion and traffic emission, which are major sources of PAHs.     

Evaluation of organochlorine and organophosphorus pesticides residues in the sediment and muscles of Nile tilapia Oreochromis niloticus (Linnaeus, 1758) fish from a River Nile Canal,Egypt

The paper reports the levels of multi-pesticide residues in the sediment and fish (Oreochromis niloticus) muscle collected from Bahr Shebeen Canal (BSC), a River Nile Canal, from September 2014 to December 2015. Samples were analysed using capillary GC chromatography, and average pesticide residue concentrations were determined. The results indicated the presence of different types of organophosphorus (OPPs) and organochlorine (OCPs) pesticides in varying degrees. Both types of residue in the sediment samples were higher than in fish muscle. The spatial and seasonal variations of OPPs and OCPs levels in sediment and fish muscle are discussed. It was found that these levels were higher than those detected from other Egyptian localities and also higher than the international permissible limits. Therefore, it is recommended to monitor the pesticide residues continuously in this, and similar, water resources to ensure the protection of the aquatic food resources.     

Concentrations, sources, and spatial distribution of individual polycyclic aromatic hydrocarbons (PAHs) in agricultural soils in the Eastern part of the EU: Poland as a case study

Soils from agricultural areas receive unsatisfactory attention as regards the contamination with organic pollutants. To answer those needs the contents of the sixteen individual PAH compounds were determined (GC/MS technique) in agricultural soils in Poland. The samples (n = 216) were collected from the upper layer of arable land in the year 2005. Half of the samples represented typical rural areas, while the rest derived from the territories potentially subjected to the urban/industrial pressure of various intensity. The mean (geometric) content of individual compounds varied from 1 μg kg^− 1 for acenaphtylene to 55 μg kg^− 1 for fluoranthene with the highest contributions (11.6%-12.9%) of phenanthrene, fluoranthene and pyrene. Higher molecular weight PAHs (4 rings) were strongly linked mutually and with the ∑16PAHs. They contributed substantially (73%) to the overall content of PAHs, which implies domination of anthropogenic sources. The calculated molecular indexes suggest that most of those PAHs derive from the combustion of coal, the main energy source in Poland. Simultaneously, the concentrations of lower molecular weight compounds seem to reflect the background, “natural” PAH compounds, which represent mainly atmospherically distributed emission. The division of the samples into groups describing geographical regions and landscape type enabled evaluation of the spatial trends in contamination of soils with PAH compounds. The most pronounced effect of spatial parameters corresponded to PAHs > 4 rings, while lower molecular weight compounds showed more homogeneous concentration through the country.