Trace metals and lanthanides in a tropical river environment

The river Periyar in the State of Kerala, India is subjected to pollution from a number of industrial units such as zinc smelter, rare earth plant, phosphatic fertilizer unit etc. The levels of Zn and Cd in water and sediments in the river have in recent years increased ten fold as compared to a study conducted earlier during 1970. The levels of these trace metals in water increase at the backwater zone under high salinity in summer due to solubilisation from the sediments. Among the lanthanides Ce is the most predominant in water. Elements such as Ce, La, Sm, Gd and Y show a concentration factor of 10³ in sediments. The trace metals show maximum concentration at the top layer of sediment column extending up to 20 cm from the surface. Particle size analysis of river sediments in the industrial outfall area shows a mass median diameter of 11 μm with a geometric standard deviation of 2.4 for Zn and Cd.     

Trace element release from estuarine sediments of South Mosquito Lagoon near Kennedy Space Center

Analytical partitioning of four trace metals in estuarine sediments collected from eight sites in South Mosquito Lagoon near Kennedy Space Center, in terms of four different categories was accomplished using four different extraction techniques. The concentrations of the four trace metals, Zn, Mn, Cd, and Cu, released in interstitial water extract, 1 N ammonium acetate extract, conc. HCl extract and fusion extract of sediments as well as their concentrations in water samples collected from the same location were determined using flame atomic absorption technique. From the analytical results the percentages of total amount of each metal distributed among four different categories, interstitial water phase, acetate extractable, acid extractable and detrital crystalline material, were determined. Our results suggest that analytical partitioning of trace metals in estuarine sediments may be used to study the mechanism of incorporation of trace metals with sediments from natural waters. A correlation between the seasonal variation in the concentration of acetate extractable trace metals in the sediment and similar variation in their concentration in water was observed. A mechanism for the release of trace metals from estuarine sediments to natural water is also suggested.     

Pollution profile of a river

A host of chemical industries subject the river to pollutants such as acids, alkalies and their salts, trace metals and radionuclides belonging to the Th and U chains. Proximity of different outfalls and poor lateral mixing in the river are responsible for high local aquatic concentrations. Scavenging reactions, in situ, and sedimentation of suspended matter result in the accumulation of radionuclides near the outfall area. Monsoon ‘flushes out’ the river into the backwater area and translocation of sediments is the major factor in the transport of pollutants.     

Estimation of Source of Heavy Metal Contamination in Sediments of Gomti River (India) using Principal Component Analysis

This study explores the extent and possible sources of heavy metal (Cd, Cr, Cu, Fe, Mn, Pb, Zn and Ni) contamination in the bed sediments of the Gomti River performing principal component analysis on the five years (Jan. 1994–Dec. 1998) data set obtained through continuous monitoring of the river water and bed sediments at eight selected sites and water/wastewater of its tributaries/drains. Influence of anthropogenic activities on metal contamination of the bed sediments was evaluated through computing the geoaccumulation index for various metals at studied sites. PCA performed on combined (river bed sediment, water, suspended solids, water/wastewater from tributaries/drains) data set extracted two significant factors explaining more than 58% of total variance. Factor loadings suggested the presence of both natural as well as anthropogenic sources for all these metals in the river bed sediments. Among all the sites, the sites 4 and 5 are more contaminated with Cd, Cu, Cr and Pb, which was supported by the geoaccumulation indices computed for metals. Factor scores revealed presence of seasonal (monsoon-related) differences in metals profiles for river water and suspended solids and absence of seasonal differences for bed sediment and wastewater. Further, the metal contamination of the bed sediment was also evaluated using biological thresholds. Results suggested that the river bed sediments are contaminated with heavy metals, which may contribute to sediment toxicity to the freshwater ecosystem of the Gomti River.     

Geochemical distribution of trace metals and organochlorine contaminants of a Lake Ontario shoreline marsh

As part of a water quality study on Rattray Marsh, a suburban marsh located on the Lake Ontario shoreline at Mississauga, Ontario, a sedimentary geochemistry study was initiated. In general, Cu, Zn, Pb and Hg were higher in concentration than in local soils, but lower than Lake Ontario recent sediments. Over the past century, an approximate two-fold increase in the sedimentary levels of Cu, Zn, Co, Cr and Ni occurred, while Cd increased nearly 4 ×, and Pb, 8 ×. No correlation was found between metals and organic carbon, and the metals appear to be associated with silts and clays as evidenced by (1) factor analysis of geochemical data, (2) higher concentrations in areas of the marsh subjected to high sediment deposition, and (3) analysis of a suspended sediment sample from Sheridan Creek, the main tributary basin of the marsh. Organochlorine contaminants include p,p¹-DDE,p,p¹-DDD,p,p¹-DDT, a-chlordane, PCB, mirex and HCB.     

Sediment trace metal contamination in the Ivory Coast,West Africa

To help expand our global perspective on trace metal contamination, concentrations of Cu, Fe, Hg, Mn, Ni, Pb, and Zn were determined for sediments from the Ebrie Lagoon in the Ivory Coast, a developing West African nation. Excess loading of several metals, especially Hg, Pb, and Zn was found at several sites. The maximum concentration of Hg measured in sediments from the Ebrie Lagoon (2250 ng g^?1) is about 30 times greater than natural levels. Similarly, Pb and Zn concentrations for the Ivorian lagoonal sediments are as high as 250 and 560 μg g^?1, respectively, showing sizeable anthropogenic inputs. Trace metal sources to the Ebrie Lagoon include untreated sewage and industrial wastes.     

The role of atmospheric deposition in an eastern U.S. deciduous forest

Atmospheric sources contributed significantly to the annual flux of trace metals and sulfate to the forest floor of Walker Branch Watershed, a forested catchment in the southeastern United States. Atmospheric deposition supplied from 14% (Mn) to≈40% (Zn, Cd, So ₄ ⁼ ) to 99% (Pb) of the annual flux to the forest floor; the remainder was attributable to internal element cycling. The measured water solubility of these metals in suspended and deposited particles indicates that they may be readily mobilized following deposition. Dry deposition constituted a major fraction of the total annual atmospheric input of Cd and Zn (≈20%), SO=(≈35%), Pb(≈55%), and Mn (≈90%); however, wet deposition rates for single events exceeded dry deposition rates by one to four orders of magnitude. Interception of rain by the canopy resulted in loss of Cd, Mn, Pb, Zn, and SO⁼ from the canopy, but uptake of H⁺ which increased with increasing free acidity of the incoming rain, and with increasing residence time of the rain on the leaf surface.     

Behavior of Metals Under Different Seasonal Conditions: Effects on the Quality of a Mexico–USA Border River

Spatial and seasonal mobilization trends of metals in surface water were evaluated in the US–Mexico San Pedro River (SPR). Water samples were collected at five sampling stations for the analysis of dissolved oxygen, pH, electric conductivity, sulfates, and metals (Cd, Cu, Fe, Mn, Pb, and Zn). Quality of the water was characterized through Ecological Criteria of Water Quality (ECWQ) established in Mexico and Water Quality Criteria (Environmental Protection Agency (EPA)). High total metal concentrations were detected as follows: Fe?>?Cu?>?Mn?>?Zn?>?Pb?>?Cd. Metal concentrations were slightly higher in dry season than in rainy season: Cd (below detection limit (BDL)–0.21 mg L^?1), Cu (BDL–13 mg L^?1), Fe (0.16–345 mg L^?1), Mn (0.12–52 mg L^?1), Pb (BDL–0.48 mg L^?1), and Zn (0.03–17.8 mg L^?1). Low pH and dissolved oxygen values as well as high sulfate content were detected in both seasons. High values of metals (Cd, Cu, Fe, Mn, Pb, Zn) were detected at station E1 representing pollution source, as well as at stations E2 (Cd, Cu, Fe, Mn), E3 (Fe, Mn, Pb), and E4 and E5 (Fe, Mn). Detected concentrations exceeded maximum permissible established in ECWQ and Water Quality Criteria (EPA). Efflorescence salts on sediments in the dry season could increase levels of metals in water column. This study provides valuable information on the potential mobility of metals in surface water of SPR located in an arid environment where transport processes are strongly linked to climate. The information derived from this study should help the regional and national authorities to address present environmental regulations.     

Annual dynamics of persistent organic pollutants in various aquatic matrices: a case study in the Morava River in Zlín district,Czech Republic

Purpose

A multi-compartment monitoring study was performed to characterize the effect of environmental variables, such as temperature and water flow as well as sediment characteristics, on the distribution and transport of persistent organic pollutants (POPs) in a dynamic river system during 1 year in an industrial region in central Europe.

Materials and methods

Waterborne polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed over a period of 1 year at five sampling sites in the Morava River in the Czech Republic. Contaminants were measured monthly in riverbed sediments, freshly deposited sediments, water samples and passive samplers.

Results and discussion

Sediments are the main carrier of POPs in the river. Distinguishable patterns of PAHs, OCPs and PCBs in sediment indicate that their origin is from distinct sources and different transport pathways. The PAHs were identified as the dominant contaminant group of compounds with a mean concentration in sediment of 5,900 μg kg^?1. Such concentrations are up to 10 times higher than in the Danube River, into which Morava drains. In contrast, mean concentrations of PCBs, hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane and its breakdown products (DDTs) and hexachlorobenzene (HCB) of 6.0, 0.4, 4.2 and 6.0 μg kg¹, respectively, are similar to those in the Danube. With some exceptions, no significant difference in composition of surficial riverbed sediments and those collected using sediment traps was observed. Despite the presence of potential local pollutant sources, the differences in contaminant concentrations between sites in the region were in most cases not significant. Variations in POP concentrations in sediments are mainly induced by high flow events, whereas seasonal variability was not observed.

Conclusions

The changes in contaminant concentrations in Morava River sediments are induced by episodic high flow events that cause erosion of contaminant-containing particles and their deposition at suitable downstream sites.     

The effect of waste water treatment on river metal concentrations: removal or enrichment?

Purpose

Discharge of untreated domestic and industrial waste in many European rivers resulted in low oxygen concentrations and contamination with trace metals, often concentrated in sediments. Under these anoxic conditions, the formation of insoluble metal sulfides is known to reduce metal availability. Nowadays, implementation of waste water treatment plants results in increasing surface water oxygen concentrations. Under these conditions, sediments can be turned from a trace metal sink into a trace metal source.

Materials and methods

In an ex situ experiment with metal contaminated sediment, we investigated the effect of surface water aeration on sediment metal sulfide (acid volatile sulfides (AVS)) concentrations and sediment metal release to the surface water. These results were compared with long-term field data, where surface water oxygen and metal concentrations, before and after the implementation of a waste water treatment plant, were compared.

Results and discussion

Aeration of surface water in the experimental setup resulted in a decrease of sediment AVS concentrations due to sulfide oxidation. Metals, known to precipitate with these sulfides, became more mobile and increasing dissolved metal (arsenic (As), cadmium (Cd), copper (Cu)) concentrations in the surface water were observed. Contrary to As, Cd, or Cu, manganese (Mn) surface water concentrations decreased in the aerated treatment. Mn ions will precipitate and accumulate in the sediment as Mn oxides under the oxic conditions. Field data, however, demonstrated a decrease of all total metal surface water concentrations with increasing oxygen concentrations following the implementation of the waste water treatment plant.

Conclusions

The gradual decrease in surface water metal concentrations in the river before the treatment started and the removal of metals in the waste water treatment process could not be countered by an increase in metal flux from the sediment as observed in the experiment.     

The Impact of Biochar Addition on Nutrient Leaching and Soil Properties from Tillage Soil Amended with Pig Manure

Poses dam in the Seine River estuary acts as receptacle of water drain-offs from highly urbanized and industrialized catchment area; therefore, this water is highly contaminated by trace metals. Most trace elements are mainly bound to particulate matter and are incorporated rapidly into the sediments. Scavenging of these metals in the sediments can be reversible due to several perturbations so as sediments also act as a source of pollutants for the overlying water. For instance, natural events (tide, flood, storm) and anthropogenic processes (water management actions) can cause disturbance of sediments and subsequent remobilization of pollutants to the water column, thereby posing a potential threat for aquatic organisms. The purpose of this study was to evaluate the mobility of trace metals by different methods in the Seine estuary sediments. The surface sediment sampled at Poses dam was characterized by high pollution level of Cd, Cu, Zn, and Pb. The estimation of metal bioavailability through ratio ΣSEM/AVS (simultaneously extracted metals/acid volatile sulfides) indicates a potential bioavailability of trace metals. The chemical partitioning using the European Community of Bureau of Reference sequential extraction method revealed that over 85, 82, and 80 % of the total Cd, Zn, and Pb, respectively, were found to be associated with the exchangeable and reducible fractions of the sediment. Another approach used consists in the quantification of dissolved metals released by sediment resuspension experiments in laboratory under controlled conditions. The results indicated that metals are released rapidly from sediment with a sharp peak at the beginning of the experiment, followed by a fast coprecipitation and/or adsorption processes on the suspended particles. Also, the Cd, Pb, and Ni mobility is higher compared to that of the other metals.     

Trace metals in a tropical river environment —speciation and biological transfer

Speciation of trace metals in the river water indicates possible organic bonding. Copper is highly complexed with the humic matter in the river sediments. Trace metals show higher levels in the milk of the cows fed on a contaminated pasture. Analysis of fish from the river shows highest enhancement in concentration for Cd. Tissuewise, the concentrations are highest in bone and liver. Calculation of the projected daily intake of trace metals, from consumer items produced locally, shows the intake of Zn and Cd to be high.     

Dissolved and particulate trace metals in a wetland of international importance: Lake Mikri Prespa,Greece

This paper reports the dissolved and particulate trace metal distributions in Lake Mikri Prespa, wetland of NW Greece. The concentrations of Cu, Pb, Zn, Cd, Al, Fe, Mn, Ni and Cr were determined in surface and hypolimnetic waters as well as in the inputs and the outflow. Trace metals were connected with two major populations of suspended particles, identified by using the recovery ratio for two different leaching reagents, namely 0.5 N HCl and 1:1 hot aqueous HNO₃. The first group is land derived entering the lake through runoff and plays a rather restricted role in its geochemistry. The second group which is more important includes authigenic carbonates, Fe and Mn hydroxides and oxides and organic rich particulates.     

Anthropogenic trace elements and polycyclic aromatic hydrocarbon levels in sediment cores from two lakes in the Adirondack acid lake region

Sediment cores were taken from the remote Sagamore and Woods Lakes in New York State's Adirondack acid lake region and analyzed for 3 to 7 ring polycyclic aromatic hydrocarbons (PAHs) and Ag, Al, As, Be, Cd, Cr, Cu, Hg, Ni, Ph, Se, Sn, TI, V, and Zn. With the exception of perylene, all of the parental PAHs, e.g. those without sidechains, and several of the metals, Pb, As, and Cd, were found to be significantly increased in the sediments of both lakes compared to their natural integrated deposits (ng cm^?2) and their background concentrations (μg g^?1 or ng g^?1 dry wt). Although the concentrations were generally much higher in Woods Lake, the total anthropogenic integrated depositions were about the same in both lakes for most of the metals and the 3 to 4 ring PAHs. The prime source of most of the 3 to 7 ring PAHs and trace elements measured is ascribed to anthropogenic combustion. Anthropogenically derived materials decreased in concentration with depth to baseline levels in sediment layers estimated by¹³⁷Cs analyses to be ～30 yr old, while biogenic or crustal derived species remained constant or fluctuated with core depth.     

Distribution of Several Heavy Metals in Tidal Flats Sediments within Bahía Blanca Estuary (Argentina)

Sediment pollution by metals is of high interest considering that it can affect marine life. The estuaries' quality may be reflected by the environmental intertidal zone condition. Subsurface sediments collected at the nude tidal flats from three sampling stations in the Bahía Blanca Estuary were analyzed for total metals concentrations (Hg, Cd, Pb, and Cr), distribution, and geochemical partitioning. Most of the elements (Hg, Cd, and Cr) have shown highest concentration values in the industrial-influenced area. Maximum value of Pb was obtained where the main freshwater input discharges. Intertidal sediments have presented higher values of Cr than the subtidal ones. Cd and Pb contents near the industrial area were strongly higher in the subtidal zones. The distribution of Cd and Pb demonstrated the occurrence of a diffusion pattern from the land toward the sea, showing a dependence on both the metal itself and/or the source. Not all studied metals have shown the highest content in the fine fraction. The chemical partitioning in the fine fractions offered evidence that the tidal flats were an important source as well as sink of metals to the adjacent coastal area. The studies of intertidal sediments provide an integrative knowledge on the potential effects of different trace metals in the environment and they must be used in the contamination studies within coastal areas.     

Heavy metal inputs to Mississippi Delta sediments

Heavy metal concentrations were determined in suspended particulates, filtered water and sediment collected in the Mississippi River and from its marine delta. More than 90% of the metal load of the river is associated with particulate matter, which is relatively constant in chemical composition with time and place. The Mississippi River suspended material is similar to average crystal rocks in Fe, Al, V, Cr, Cu, Co, Mn, and Ni concentration but is generally enriched in Zn, Cd and Pb. Sediment cores dated by the Pb 210 method show that the Cd and Pb enrichments are recent phenomenon and are most likely due to the activities of man. About 6000 tonne of Pb and 300 tonne of Cd are being added to the delta sediments by man each year, more than 30 times the amount added to the Southern California Bight. River particulate matter is essentially identical to deltaic sediments in Al, Fe, Cr, V, Cd and Pb concentration, but the sediments are depleted in Co, Cu, Mn, Ni and Zn by 20 to 40%. Chemical leaching of the solids show the metal losses to be primarily from the oxide phase, suggesting diagenetic reduction and mobilization as a mechanism. Trace metal concentrations in filtered Mississippi River water were below the limits for safe drinking water and were similar to world average river values. The abundant river suspended matter and high pH combine to keep dissolved trace metal concentrations low.     

Concentration and deposition of trace metals in Ontario-1982

Results of trace metal concentrations in air and precipitation and the corresponding wet and dry deposition in Ontario in 1982 arc reported. In terms of the spatial patterns, in general, there was a decreasing gradient from south-to-north in both concentration and deposition. Patterns differed with each parameter although certain groups of metals (e.g., Fe and Al; Pb, Zn, and Mn) displayed similar patterns. In general, wet deposition was greater than dry deposition at all sites. Geographically, the variability in the wet to dry deposition ratio for coarse particles (MMD > 2.5 μm) was small. However, it increased from the south to the north for fine particles (MMD < 2.5 μm), being higher away from the source areas. Scavenging ratios (W) have been derived from the precipitation and air concentrations of trace metals. The scatter in W is quite large for all trace metals, up to 2 orders of magnitude. There was little seasonal variability in W for fine particles (Pb, Mn, Zn, and Cd). However, coarse particles (Fe, Al, and Cu) were more efficiently scavenged by snow than by rain.     

Temporal changes in metal levels of the lichens Parmotrema praesorediosum and Ramalina stenospora,Southwest Louisiana

Two species of lichen native to southwest Lousiana, Parmotrema praesorediosum (Nyl.) Hale and Ramalina stenospora, Mull. Arg. have been investigated as air pollution monitors. Over the period 1983–88 samples were collected at 18 stations in the Lake Charles/Westlake/Sulphur area. The samples were analyzed for A1, Fe, Cu, Pb, Cd, Hg, Cr, and Zn. When metal concentrations in lichens were plotted vs year for certain representative stations, a dramatic reduction in the concentrations of certain metals was seen after 1983. When the most recent data are compared with those previously obtained, the effects of the industrial zone, which was previously demonstrated, have now all but disappeared.     

Groundwater Contribution of Metals from an Abandoned Mine to The North Fork of The American Fork River, Utah

Surface water discharge measurements and metals concentrations in the North Fork of the American Fork River, Utah, its tributaries, and the groundwater in the vicinity of the Pacific Mine were used to evaluate the impact of groundwater on loading rates of metals and As to the river. Fish in the river contain As, Cd, and Pb at concentrations that are hazardous to human health if consumed. The results suggest that dissolved As, Cd, Cu, Fe, Mn, Pb, and Zn enter the river when it is a gaining stream. However, the suspended metals load is significantly greater than the dissolved load, and generally decreases through the reach of river adjacent to the mine site. Cadmium and Mn travel as dissolved species while Cu, Fe, Pb, and Zn travel as suspended solids. Arsenic seems to travel both with the suspended solids and in the dissolved state. The geochemical modeling program PHREEQC and a diffuse double layer surface complexation model were used to investigate the chemical controls on metals mobility and attenuation in the surface and groundwaters at the site. Based on the PHREEQC results, the most important process in these waters is the precipitation of ferrihydrite, also referred to as hydrous ferric oxide (HFO). Copper, Pb, most importantly Zn, and to a lesser degree As sorb to HFO.     

Algal Blooms in the Darling-Barwon River, Australia

Australian waterbodies have long water residence times, stratification is common, and eutrophication is driven mainly by the internal loads. The 1991 blue-green algal bloom on the Darling-Barwon River was at a time of low river flow (～100's ML/day) and hot/still conditions. The sustained low flow allowed significant influx of a sulfate-rich saline groundwater and this caused clay flocculation, water clarification and increased photosynthesis in the surface water, and increased sulfate reduction, pyrite formation and Fe mobilisation in anoxic bottom sediments. Since this time similar optimum bloom periods have not produced blooms, or Fe mobilisation, despite high soluble P concentrations. Algal growth during optimum bloom periods is known to be N-limited and it is possible that, in this case, essential trace elements are limiting N-fixation — clay flocculation is a very efficient process of removing trace elements from the water column. Optimum bloom periods can potentially set up a feed-back involving the bottom sediments and increasing sulfate concentration, to resupply surface water with P and trace metals. It is suggested that this operated in late 1991, but not during later optimum bloom periods as no further Fe mobilisation is recorded. The management implication is to maintain sufficient river flow to prevent any significant groundwater influx.