Mercury distribution and exchanges between the Amazon River and connected floodplain lakes

This work presents the distribution and the partition of mercury (Hg) in the Curuai floodplain lakes along the Amazon River. The maximum Total Filtered Hg (T-FHg) concentrations in the floodplain lakes (28 to 52 pmol L^− 1) coincide with the maximum T-FHg concentrations of the Amazon River and are measured during the flooding period. The lowest T-FHg values (3 to 5 pmol L^− 1) are observed during the flood peak of the mainstream, during the rainy season, when waters are diluted by the local rainfall. In this system, Hg is mainly transported in the particulate phase, confirmed by elevated values of the Hg partition coefficient (4.77 < K_d (Hg) < 5.83 L kg^− 1). The highest Total Particulate Hg (T-PHg) concentrations (47–478 pmol L^− 1) in the lakes are measured during the dry season when they are isolated from the mainstream. This enrichment is due to the elevated TSS content associated to the re-suspension of the bottom sediments by the wind action and the bioturbation in shallow water lakes.In the flooded system, the lakes show different geochemical characteristics that control the Hg distribution and partition. In the white water (WW) lakes, characterized by oxidative neutral waters and highest TSS contents (till 2041 mg L^− 1), the T-PHg is associated to the particulate organic matter mainly during the dry season, while the T-FHg and T-FMn concentrations are correlated. In the black water (BW) lakes that show reductive pH conditions and lowest TSS load (2 to 52 mg L^− 1), P-iron and T-PHg display a positive relationship whereas the redox conditions favor the desorption of Hg from the particulate to the filtered phase.The mercury mass budget estimated in this study confirms that the Curuai floodplain system acts as a particulate mercury trap, with a net storage of particulate Hg of 150 kg PHg year^− 1.     

Particulate and dissolved trace metals in Lake Ontario

Particulate metal concentrations in the nearshore waters of Lake Ontario have been determined to be 690 ng l⁻¹ for Cu; 40 ng l⁻¹ for Cd; 180 ng l⁻¹ for Ni; 1690 ng l⁻¹ for Zn; 2100 ng l⁻¹ for Mn; and 700 μg l⁻¹ for Fe. These values are considerably higher than the particulate metal concentrations in the offshore waters: 130, 8, 34, 230, 110, 260 and 9000 ng l⁻¹ for Cu, Cd, Ni, Zn, Pb, Mn and Fe respectively. In general, 50–80% of the Cu, 10–40% of the Ni, 20–60% of the Cd and >60% of the Pb in the lake water were bound to the suspended particulates. From the standing crop of the particulate metals and the estimated rates of their deposition on the lake bottom, the residence times of the particulate metals in the lake water column have been estimated to be about 0.5 yr. on the average. The suggestion is made that particulate organic matter may be an important vehicle for metal transport to the Lake Ontario sediments.     

Comparative study on organic constituents in polluted and unpolluted inland aquatic environments-I features of hydrocarbons for polluted and unpolluted waters

The constituents of hydrocarbons between highly polluted river waters collected from the Tokyo area and unpolluted river, brook, reservoir and pond waters obtained from the Ogasawara (Bonin) Islands were compared to characterize their features for polluted and unpolluted waters. n-Alkanes between the carbon chain length of C₁₂ and C₃₆, squalane and unresolved complex mixture of hydrocarbons (UCMH) were found in most of the river waters of the Tokyo area at the contents ranging from 0.026 to 14 μg 1⁻¹, from 0.004 to 1.7 μg 1⁻¹ and from less than 5 to 290 μg 1⁻¹, respectively, whereas in the waters of the Ogasawara Islands, only n-alkanes ranging from C₁₃ to C₃₇ were found with the great predominance of odd-carbon numbers at the contents varying from 0.042 to 4.0 μg 1⁻¹.It was indicated that the presence of squalane, UCMH and even-carbon numbered n-alkanes as the major constituents are intimately correlated with artificial hydrocarbon sources (fossil fuels and their products and both combustion products, and industrial products), while the great predominance of odd-carbon numbered n-alkanes for the unpolluted areas are mainly due to algae and higher plants. Besides, the major portion of n-alkanes, squalane and UCMH are thought to be present in polluted and unpolluted waters associated with particulate materials.     

Comparative study on organic constituents in polluted and unpolluted inland aquatic environments—II: Features of fatty acids for polluted and unpolluted waters

Fatty acids were analyzed for polluted river waters from the Tokyo area and unpolluted river, brook, reservoir and pond waters from the Ogasawara (Bonin) Islands to elucidate their features for polluted and unpolluted waters. Fatty acids ranging from the carbon chain length of C₈-C₃₄ including unsaturated and branched acids were found with the great predominance of even-carbon numbers and lower molecular weight ranges (C₁₃–C₁₉) in the water samples from the Tokyo area and Ogasawara Islands. It was thus confirmed that no marked changes in fatty acid composition between polluted and unpolluted waters are absent. However, the total contents of the acids (average, 270 ± 120 μg 1⁻¹ at 90% confidence limits) as well as the FAC (fatty acids as carbon)/TOC (total organic carbon, 2.6 ± 0.93%) and FAC/EOC (extractable organic carbon with ethyl acetate, 16 ± 6.7%) of river water samples from the Tokyo area were considerably higher than those of the waters from the Ogasawara Islands (58 ± 29 μg 1⁻¹, 0.79 ± 0.48% and 2.1 ± 0.51%, respectively). These higher values for the Tokyo area should be due to sewage.A filtering method showed that most of fatty acids (>95%) was present in particulate fractions. In addition, the content of free fatty acids was fairly lower than that of combined fatty acids. Further, unsaturated fatty acids were detected only in combined forms both in particulate and dissolved fractions. They are considered to be present as esters in polluted and unpolluted waters.     

Mercury distribution in waters and fishes of the upper Madeira rivers and mercury exposure in riparian Amazonian populations

In this paper, the results of mercury concentrations in two abiotic compartments (river water and suspended particles) and two biotic compartments (fish and human hair) from the upper Madeira rivers of the Bolivian Amazon basin are presented. Because of the local hydrological regimes and a high deposition rate in the plain, due to the presence of a subsidence zone at the bottom of the Andean piedmont, in the dry season, the highest mercury concentrations and fluxes were not found in rivers where mining activities took place (2.25–6.99 ng l⁻¹; and 1.07–8.67 mg Hg d⁻¹ km⁻²), but at the outlet of the Andean basins exploited for their alluvial gold (7.22–8.22 ng l⁻¹; and 9.47–9.52 mg Hg d⁻¹ km⁻²). The total mercury concentrations measured in surface waters of the upper Beni basin varied during the dry season, from 2.24 to 2.57 ng l⁻¹ in the glacial waters of the Zongo river, to 7.00 ng l⁻¹ in the Madeira River at Porto Velho and 9.49–10.86 ng l⁻¹ at its confluence with the Amazon. The results obtained from fish indicate, on one hand, that 86% of the piscivorous fishes collected in the Beni river were contaminated, and, on the other hand, their high mercury concentrations could exceed by almost four times the WHO (1976) safety limit. In the Beni River, the mercury concentrations found in omnivorous and mud-feeding fish ranged from 0.02 to 0.19 μg g⁻¹ (wet wt.), and in piscivorous fish, from 0.33 to 2.30 μg Hg g⁻¹ (wet wt.). The mercury accumulated by carnivorous fishes was mainly present in its organic form; methylmercury represented 73–98% of the total mercury analysed. Eighty persons were studied in the entire Bolivian Amazonian basin. Unlike the gold miners, who are more affected by tropical diseases, such as malaria and yellow fever, the indigenous people living on the banks of the Beni river, present elevated levels of mercury (9.81 μg g⁻¹ on average). We observed an increase in contamination in young children still being breast-fed, confirming that hair mercury concentration in babies was significantly affected by maternal mercury contamination during pregnancy. These results show that the major health impacts caused by mercury affect people who are not working directly in gold mining activities but who have a regular fish diet.     

Seasonal changes in the forms and species of iron and manganese in a seasonally-inundated floodplain swamp

The forms and species in which Fe and Mn occurred in a seasonally-inundated Southeastern United States floodplain swamp were examined. The analytical scheme provided operational estimates of the concentrations of Fe(II), Fe(III) and Mn in particulate (> 0.45 μm), colloidal (0.45-0.0032 μm) and ultrafilterable (<0.0032 μm) size fractions. The procedure also provided a differentiation between forms of Fe that were readily reactive to bathophenanthroline (BPN) and those forms that were unreactive to BPN until undergoing acid extraction. Further, the concentrations of Fe and Mn associated with suspended particulate matter in ion-exchangeable, reducible, and oxidizable forms and as inert mineral were determined using an operational classification scheme.The ferric species predominated due to the oxygenated conditions of the swamp water. Concentrations of colloidal-sized, readily-reducible Fe and of ultrafilterable Fe(II) and Fe(III) were low (<0.25 mg 1⁻¹) and fairly constant throughout the study; more Fe occurred in the colloidal than ultrafilterable size range. The majority of the colloidal-sized Fe was in an acid-extracted form. Almost all ultrafilterable Fe was ferric, although high Fe(II) concentrations occurred in floodplain soil pore water. Total Fe, mainly particulate-associated, varied with periods of flooding and intense bioturbation. Manganese occurred in low concentrations, primarily in the ultrafilterable fraction, although colloidal-sized Mn forms were important at times. Most of the Fe and Mn associated with suspended particulates occurred in the inert mineral form and to a lesser extent in a reducible form. Ion-exchangeable and oxidizable particulate Fe and Mn were relatively unimportant.     

Flameless atomic absorption analyses of mercury in model aquatic systems

Chemical models of freshwater and seawater (34‰ S) have been used to examine the effect of humic material on the analysis of mercury by flameless atomic absorption spectrometry. Solutions containing mercuric chloride (1 μg Hg 1⁻¹) and various concentrations of humic material were allowed to attain equilibrium under carefully controlled conditions. In both media, association between the inorganic and organic entities took place within 90 min at pH ≥ 7 and the organically bound mercury was not detected by an analytical method designed for inorganic mercury. The amount of detectable mercury was related to the quantity of humic material added to the solutions.In experiments involving changes of pH the model solutions showed three characteristics: (1) a flat response in the neutral and alkaline pH range, where the humates are apparently stable; (2) a minima in the pH range 2–4 where the formation of an acid flocculent appears to remove additional mercury from solution: (3) at pH = 1, some release of mercury occurs from the organic precipitate.Photolysis studies using the model freshwater solutions showed that total mercury measurements could be made after 2 h irradiation at pH = 1. Using the same technique methylmercury chloride and diphenylmercury decomposed within 1 h. These results are relevant to routine and analyses of total mercury in natural waters.     

The role of suspended solids in the estuarine geochemistry of mercury

The behaviour of mercury in total water (soluble + particulate fractions) and suspended solids of the surface waters of the Wyre estuary, northwest England, has been studied during a tidal cycle. The estuary is contaminated by mercury derived from chlor-alkali effluents and other sources. The results from eight stations in the estuary show that quantitatively mercury in suspended solids dominates the mercury budget of the estuarine waters. At high chlorinity periods in the tidal cycle the mercury concentrations in suspended solids decreased significantly, and can be related to changes in the specific surface area and organic carbon contents of the suspended matter. A very good correlation between mercury and organic carbon concentrations in the suspended solids exists, and laboratory experiments support the conclusion that mercury is mainly associated with the organic phase of the suspended material and is not easily chemically desorbed during estuarine mixing processes.     

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.     

Nitrate determination in fresh and some estuarine waters by ultraviolet light absorption: A new proposed method

The new proposed u.v./resin technique for nitrate determination is either not affected by, or can allow for, the following interfering chemicals at levels occurring in natural polluted or unpolluted waters; chloride, phosphate, sulphate, carbonate/bicarbonate, bromide, nitrite, coloured metal complexes, humic acids, ammonium, dyes, detergents, phenol and other u.v. absorbing organics. The method is quick and has an accuracy of ±3%. Concentrations of NO₃.N in the range 0.1–3.0 mg l⁻¹ can be determined in fresh water. Concentration of the sample to determine lower levels by evaporation is feasible with certain upland waters but should not be attempted if the sample has a high humic acid concentration. The technique can only be used in nitrate rich estuarine and coastal waters because the lower limit of detection is raised to 0.5 mg l⁻¹ when the sample is diluted to remove bromide interference.     

Survey of volatile halogenated organics (VHO) in Italy: Levels of VHO in drinking waters, surface waters and swimming pools

A survey undertaken in Italy (Emilia-Romagna region) has shown that Volatile Halogenated Organics (VHO) are present in many water samples; analysis has been performed by static head-space gas chromatographic technique.In drinking water samples low levels of pollution have become evident before any treatment, while after chlorination with sodium hypochlorite, or chlorine as a gas, VHO have appeared, almost exclusively as trihalomethanes (THM), sometimes at fairly high levels (max = 41.8 μg l⁻¹).Surface water samples have been collected every other month in one year, and have shown different levels of contamination; in most cases VHO (mainly chlorinated solvents) appeared just as traces, seldom at high concentration (max = 263 μg l⁻¹).Swimming pool samples have shown the high levels of contamination (max = 177.4 μg l⁻¹), mainly due to THM, as a consequence of chlorination with sodium hypochlorite.As a matter of fact, it has become evident that VHO pollution is wide-spread in every kind of water; while contamination of surface waters can only involve environmental and aquatic life, contamination especially of drinking waters, and also of swimming pool waters must be controlled as it can directly act on human health.     

Some elements comprising particulate matter during summer in waters of various environments in British Columbia, Canada

Multi-elemental traces comprising particulate matter in natural water collected during summer in 1978 and 1979 from British Columbia, Canada, were analyzed by α-particle excited X-ray fluorometry. Common elements from all waters examined were Si, Cl, Ca and Fe. The similarity of their distribution in different aquatic environments was statistically analyzed. They were distributed homogeneously in the marine environment but heterogeneously in the freshwater environments. No heavy metals concerned with the environmental standards were detected for all waters examined.     

Binding capacity of wastewater discharge to seawater

The copper binding capacity was used to follow physico-chemical changes in the mixing of sewage effluent and seawater. In laboratory experiments dilute aliquots of filtered and unfiltered effluents were mixed with artificial seawater to give saline concentrations of between 0 and 40‰. The copper binding capacity of the filtered sample decreased rapidly from 22.8 to 0 μg l⁻¹ in the salinity range 5–10‰. The difference between the unfiltered and filtered binding capacity, defined as the adsorption capacity, varied from 28.5 to 0 μg l⁻¹ in the salinity range 15–22‰. These results were interpreted in terms of destabilisation of copper associations with humates, colloids and particulate matter with increasing salinity. The behaviour of unfiltered binding capacity in the effluent plume was measured and the results showed reasonable agreement with results from the laboratory experiments.     

The use of uric acid as a method of tracing domestic sewage discharges in riverine, estuarine and coastal water environments

The chemical tracking of sewage effluents discharged into fresh and saline waters presents difficulties, especially in estuaries. The main difficulty is caused by the dissolved constituents being used to monitor the effluent also occurring naturally at similar levels. Uric acid is present at significant levels in untreated sewage and is not normally found in unpolluted waters. Until now no suitable routine method has been available for uric acid estimation in fresh and saline waters at levels normally encountered in the environment. In this paper we describe a recently developed technique using high-performance liquid chromatography which estimates uric acid in both fresh and saline waters in the range 1–10,000 μg l⁻¹ with a precision (2σ) of ±20% at 2 μg l⁻¹, ±4% at 40 μg l⁻¹ and ±2% at 10 mg l⁻¹.     

Iron and manganese oxides in Finnish ground water treatment plants

Large amounts of ochreous precipitates are formed on aeration of Fe containing Finnish ground waters during purification for drinking purposes. Sixty-four precipitates were characterized chemically and mineralogically. X-ray diffraction (XRD) indicated that the Fe-rich precipitates consist mainly of a poorly ordered ferrihydrite (5 Fe₂O₃ · 9 H₂O) which only has 2–3 of the 6 XRD lines characteristic of better ordered ferrihydrite. The surface area ranges between 325 and 433 m² g⁻¹ corresponding to a particle size of 5 nm. The ferrihydrites contain 3–7% Si strongly associated with the ferrihydrite as indicated by an i.r. absorption band at 960–975 cm⁻¹ which is associated to Fe-O-Si bonds. Si-containing ferrihydrite typically forms by rapid oxidation of ground waters with 1–23 mg 1⁻¹ Fe and 7–12 mg 1⁻¹ Si at pH 6–7. Very similar products formed in a simulation experiment in which artificial ground water with 20 mg 1⁻¹ Fe was oxidized in the presence of 12 mg 1⁻¹ Si. A1 < 4 mg 1⁻¹ Si lepidocrocite (γ-FeOOH) was formed showing that Si in the system prevents the formation of the more stable and better crystallized FeOOH forms. A transformation of 2-line ferrihydrite to better ordered ferrihydrite or goethite with time is indicated. The Mn-oxide birnessite was identified in black precipitates formed in one plant.     

Phosphorus adsorption to riverine suspended matter: Implications for the P-budget of Lake Constance

Dissolved phosphorus from Lake Constance water was adsorbed by particulate matter from the Alpenrhein whenever the equilibrium phosphorus concentration of 0.85 μmol l⁻¹ was exceeded. When shaken in phosphate-free lake water the solids liberated small amounts of P (1% of the total-P). The maximum adsorption capacity of the particles was estimated to be 2.8 μmol g⁻¹ (dry substance). Only part of the phosphorus once experimentally sorbed to the solids was shown to desorbe in P-free lake water.During 1981 1.47·10⁹ kg of particulate matter was discharged into Lake Constance from the Alpenrhein. By adsorption these sedimenting materials had the potential to remove 18–25·10³ kg of dissolved phosphorus from the water column, thus comprising almost 2% of the total P-load in 1981.     

Dissolved mercury in the Lake Windermere catchment area

Typical dissolved mercury (Hg) concentrations in unpolluted waters are alleged to be < 50 ng 1⁻¹ and sometimes< 10 ng 1⁻¹. Mean concentrations found in the catchment area of Lake Windermere were found to range between 12 and 29 ng 1⁻¹ over a three month period. However in particular instances concentrations of 75 and 96 ng 1⁻¹ were found, thought to be due to runoff from mineral deposits and sewage outfalls respectively.     

Dissolved organic matter and the dissipation of chlorine in estuarine water and seawater

Dissolved organic matter in estuarine water and seawater collected in the summers of 1980 and 1981 in the James River, Virginia and the mouth of Chesapeake Bay were separated into fractions according to their nominal molecular weights (NMW) by ultrafiltration. Estuarine waters contained higher concentrations of dissolved organic carbon (DOC). Among the fractions, between 66–89% of the DOC was found in the fraction with NMW below 10,000. Estuarine waters also had higher chlorine demands. At a dose of 5 mg l⁻¹, in 23 h, about 90% of the added chlorine disappeared in estuarine waters, whereas, in seawater, only 60–75% of the chlorine had dissipated. At least two-thirds of the chlorine demand occurred in the first 5 h. About 10–30% of the chlorine demand may be attributed to the fraction with NMW above 10,000. The remaining chlorine demand was distributed almost equally between the fractions with ranges of NMW of 1000–10,000 and below 1000. If reactivity is measured in terms of organic chlorine demand (ΔClo) per unit weight of DOC, the fractions with lower NMW (< 1000 and 1000–10,000) always had a higher reactivity towards chlorine. Between these two fractions, the one with NMW between 1000 and 10,000 exhibited higher reactivity more frequently. The highest reactivity found was 1.4 mg ΔClo mg⁻¹ DOC.     

Cadmium in the Rhône river

The distribution of cadmium in the Rhône river was studied using differential pulse anodic stripping voltametry with a static mercury drop electrode. For 11 potentially contaminated river stations, the Cd in true solution averaged 39 ± 23 ng kg⁻¹, adsorbed on suspended matter was 19 ± 22 ng kg⁻¹ (liquid phase) and suspended matter content was 2.4 ± 1.5 mg kg⁻¹ (solid phase), equivalent to 40 ± 24, 22 ± 24 and 38 ± 31%, respectively, of the total carried under these conditions. For sediments the mean Cd content was 0.9 ± 0.6 mg kg⁻¹. The water values are low by world standards, even though sampling was biased towards sites potentially contaminated. This could be partially due to the unusual water pH of 7.8–8.5.     

Concentrations of particulate mercury in the Atlantic marine atmosphere

The concentrations of mercury have been determined in atmospheric particulates collected by a shipboard filter method from locations over the North and South Atlantic Ocean. In the North Atlantic westerlies at 57°N the geometric mean mercury concentration was 0.035 ng (SCM)^?1, whilst at middle and low latitude the mean was 0.011 ng (SCM)^?1. A geometric mean concentration of 0.007 ng (SCM)^?1 was observed in the South Atlantic. The interhemispheric differences in concentration were interpreted as reflecting variations in the anthropogenic contribution to the marine aerosol. The results were used to estimate the flux of mercury to Atlantic surface waters. An upper limit for the flux of mercury from the atmosphere to the North Atlantic was calculated to be between 600-380 t yr^?1 and 150-100 t yr^?1 for the South Atlantic.