Mercury Speciation in the Water of Minamata Bay, Japan

The speciation of mercury (Hg) in Minamata Bay (Japan) was studied over a 2-year period (2006?C2008). Concentrations of dissolved total Hg, dissolved methylmercury (MeHg), particulate total Hg, and suspended solids were 0.43?±?0.14 ng/l (mean?±?standard deviation), 0.10?±?0.06 ng/l, 3.04?±?2.96 ng/l, and 5.94?±?2.10 mg/l, respectively. Correlations between concentrations of particulate total Hg and suspended solids at four depths (surface: 0 m; mid-depth: ?6 m, ?10 m; and bottom +1 m layer) were only significant in the bottom +1 m layer. The mean dissolved MeHg concentration and the ratio of dissolved MeHg to dissolved total Hg were considerably higher in summer compared to other seasons. The data suggest that bottom sediment was not the sole source of MeHg, and that MeHg may be produced in the water column by the conversion of divalent Hg eluted from resuspended bottom sediment. The correlation between seawater characteristics such as salinity, temperature, dissolved oxygen (DO), and dissolved MeHg concentration indicates that Hg methylation could be influenced by the heterotrophic activity of microorganisms in the seawater. In particular, inverse correlations were observed between DO, salinity, and MeHg concentration. However, dissolved MeHg concentrations did not correlate with seawater characteristics such as pH or chlorophyll-a.     

Seasonal Variations of Ten Metals in Highway Runoff and their Partition between Dissolved and Particulate Matter

Knowledge of differentiation of pollutants in urban runoff between dissolved and particulate matter is of great concern for a successful design of a water treatment process. Seasonal variations in pollutant load are of equal importance. Ten metals (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), as dissolved and particulate bound, was studied in the runoff from a major urban highway during a winter season and its following summer. Studded tyres and winter salting were expected to have an impact on the runoff water quality. The dissolved part of Al, Cd, Co, Cr, Mn and Ni was significantly higher in winter in comparison with summer (p?<?0.01). For Fe, however, the dissolved part was lower during winter. No significant difference was found for Cu, Pb and Zn between the two seasons. The mass concentration (mg kg^?1) for all metals was significantly higher over the summer except for Al and Co, which showed a higher mass concentration during the winter. The concentration of selected metals vs. total suspended solids (TSS) showed a linear relationship (r ²?>?0.95) during winter runoff events except for Cd. A good correlation (r ²?>?0.90) was also found for the summer period for Al, Cu, Fe, Mn, Ni and Zn. It is suggested that the metal pollutant load during winter could be assessed indirectly by measurement of TSS.     

Effects of combined sewer overflows and storm water drains on metal bioavailability in small urban streams (Prague metropolitan area,Czech Republic)

Purpose

The aims of the study were to evaluate the effect of combined sewer overflows (CSO) and storm water drains (SWD) on metal bioavailability in small urban streams in Prague and to evaluate levels of metals in water, sediment, and macroinvertebrates. The following working hypotheses were adopted: (a) sites dominantly affected by SWD are less polluted by metals, and (b) sites dominantly affected by SWD have higher bioavailability of metals.

Materials and methods

Physical and chemical parameters (pH, conductivity, NO₃-N, NH₄-N, COD, alkalinity, and water hardness) and concentrations of the metals Cu, Zn, Pb, Ni, and Cr were determined in samples of water and sediment at five to six sites on four target streams—Záti?ský Creek, Ko?íkovský Creek, Boti? Creek, and Rokytka Creek—three to five times per year during the period 2002–2004. The sites from all studied creeks were categorized into five groups according to the prevailing type of urban drainage impact. Macroinvertebrates were sampled and analyzed for metals at each site for a period of 1 month. The concentration patterns of metals were interpreted by partition coefficient (Kd), hazard quotient (HQ), cumulative criterion unit (CCU), and biota sediment accumulation factor (BSAF).

Results and discussion

Concentrations of metals in water as well as in sediment at sites receiving water from SWD were lower than at sites where creeks receive water from CSO, except for Pb. Concentrations of Cu, Zn, and Pb in sediment were higher at sites affected by CSO. Concentrations of metals in aquatic macroinvertebrates, expressed as BSAF, indicated higher values at sites affected by SWD. Frequencies of high BSAF (>1) were lower in CSO compared to SWD. This finding was explained by (a) a decrease of pH on SWD sites compared to the increase of pH on CSO sites during rain events, (b) a greater resuspension of sediment at SWD sites during rain events, and (c) an abundance of organic matter in CSO available for sorption of metals and a corresponding reduction of their bioavailability.

Conclusions

In the study area, the type of urban drainage affects the bioavailability of metals—while SWD increase metal bioavailability, CSO cause its decrease. The sediments in SWD sites do not indicate risk to the benthic community according to the applied environmental quality standards. Water and sediment in creeks affected by SWD are less polluted by metals. Both working hypotheses were therefore supported.

     

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.     

Role of Hydrous Iron Oxide Formation in Attenuation and Diel Cycling of Dissolved Trace Metals in a Stream Affected by Acid Rock Drainage

Mining-impacted streams have been shown to undergo diel (24-h) fluctuations in concentrations of major and trace elements. Fisher Creek in south-central Montana, USA receives acid rock drainage (ARD) from natural and mining-related sources. A previous diel field study found substantial changes in dissolved metal concentrations at three sites with differing pH regimes during a 24-h period in August 2002. The current work discusses follow-up field sampling of Fisher Creek as well as field and laboratory experiments that examine in greater detail the underlying processes involved in the observed diel concentration changes. The field experiments employed in-stream chambers that were either transparent or opaque to light, filled with stream water and sediment (cobbles coated with hydrous Fe and Al oxides), and placed in the stream to maintain the same temperature. Three sets of laboratory experiments were performed: (1) equilibration of a Cu(II) and Zn(II) containing solution with Fisher Creek stream sediment at pH 6.9 and different temperatures; (2) titration of Fisher Creek water from pH 3.1 to 7 under four different isothermal conditions; and (3) analysis of the effects of temperature on the interaction of an Fe(II) containing solution with Fisher Creek stream sediment under non-oxidizing conditions. Results of these studies are consistent with a model in which Cu, Fe(II), and to a lesser extent Zn, are adsorbed or co-precipitated with hydrous Fe and Al oxides as the pH of Fisher Creek increases from 5.3 to 7.0. The extent of metal attenuation is strongly temperature-dependent, being more pronounced in warm vs. cold water. Furthermore, the sorption/co-precipitation process is shown to be irreversible; once the Cu, Zn, and Fe(II) are removed from solution in warm water, a decrease in temperature does not release the metals back to the water column.     

Dissolved Organic Carbon in Association with Water Soluble Nutrients and Metals in Soils from Lake Okeechobee Watershed, South Florida

Water quality of Lake Okeechobee has been a major environmental concern for many years. Transport of dissolved organic matter (DOM) in runoff water from watershed is critical to the increased inputs of nutrients (N and P) and metals (Cu and Zn). In this study, 124 soil samples were collected with varying soil types, land uses, and soil depths in Lake Okeechobee watershed and analyzed for water-extractable C, N, P, and metals to examine the relationship between dissolved organic carbon (DOC) and water soluble nutrients (N and P) and metals in the soils. DOC in the soils was in 27.64?C400 mg kg^?1 (69.30 mg kg^?1 in average) and varied with soil types, land uses, and soil depth. The highest water-extractable DOC was found in soils collected in sugar cane and field crops (277 and 244 mg kg^?1 in average, respectively). Water soluble concentrations of N and P were in the range of 6.46?C129 and 0.02?C60.79 mg kg^?1, respectively. The ratios of water-extractable C/N and C/P in soils were in 0.68?C12.52 (3.23 in average) and 3.19?C2,329 (216 in average), and varied with land uses. The lowest water-extractable C/N was observed in the soils from dairy (1.66), resident (1.79), and coniferous forest (4.49), whereas the lowest water-extractable C/P was with the land uses of dairy (13.1) and citrus (33.7). Therefore, N and P in the soils under these land uses may have high availability and leaching potential. The concentrations of water soluble Co, Cr, Cu, Ni, and Zn were in the ranges of?<?method detection limit (MDL)?C0.33, <MDL?C0.53, 0.04?C2.42, <MDL?C0.71, and 0.09?C1.13 mg kg^?1, with corresponding mean values of 0.02, 0.01, 0.50, 0.07, and 0.37 mg kg^?1, respectively. The highest water soluble Co (0.10 mg kg^?1), Cr (0.26 mg kg^?1), Ni (0.31 mg kg^?1), and Zn (0.80 mg kg^?1) were observed in soils under the land use of sugar cane, whereas the highest Cu (1.50 mg kg^?1) was with field crop. The concentration of DOC was positively correlated with total organic carbon (TOC) (P <0.01), water soluble N (P <0.01), electrical conductivity (EC, P <0.01), and water soluble Co, Cr, Ni, and Zn (P <0.01), and Cu (P <0.05), whereas water soluble N was positively correlated with water soluble P, Cu, and Zn (P <0.01) in soils. These results indicate that the transport of DOC from land to water bodies may correlate with the loss of macro-nutrients (N, P), micro-nutrients (Cu, Zn, and Ni), and contaminants (Cr and Co) as well.     

Trace metals in the soils of Water Conservation Area of Florida Everglades: Considerations for ecosystem restoration

Purpose

Inorganic contaminants present a major challenge for the restoration of aquatic ecosystems. The objectives of this study were to determine the extent of trace metal contamination and investigate the influence of different plant communities on trace metal accumulation in the soils of the Florida Everglades.

Materials and methods

Soil samples (n?=?117) were collected from 0 to 10-cm depth using a stainless steel coring device from sites with three dominant plant communities—cattail, sawgrass, and slough—of Water Conservation Area-2A (43,281 ha) of Florida Everglades.

Results and discussion

The mean pH in soils collected from three plant communities was 6.75–6.82, whereas electrical conductivity was slightly greater in the sawgrass (0.69 dS m^?1) than cattail (0.58 dS m^?1) and slough (0.40 dS m^?1). Mean reduction–oxidation potential was greatest in cattail (?113 mV) than sawgrass (?85.3 mV) and slough (?48.3 mV) soils. Among 11 trace metals (As, B, Co, Cr, Cu, Mn, Mo, Na, Ni, Pb, Zn) found in soil samples, Na had the greatest contents and was greater in cattail (2070 mg kg^?1) and sawgrass (1735 mg kg^?1) than slough (1297 mg kg^?1). Four trace metals (B, Cu, Mo, Ni) were significantly greater in cattail than sawgrass and slough. Whereas, Mn was significantly lower in cattail (31 mg kg^?1) than both sawgrass (84 mg kg^?1) and slough (51 mg kg^?1). Cattail also had significantly lower Cr (1.97 mg kg^?1) and Pb (10 mg kg^?1) than sawgrass (Cr 2.5 mg kg^?1; Pb 20.8 mg kg^?1). As (<6.9 mg kg^?1), Co (<1.3 mg kg^?1), and Zn (<17.2 mg kg^?1) were not significantly different among soils collected from three plant community-dominant sites. Contents of Cd and Se were below the method detection limits (Cd 0.01 mg L^?1; Se 0.2 mg L^?1) and are not reported.

Conclusions

None of the trace metals in the soils exceeded the US Environmental Protection Agency sediment toxicity thresholds. Results from this study provided baseline concentrations of trace metals, which can be used to measure the success of restoration efforts in Florida Everglades.

     

Removal of Zinc from Tidal Water by Sediments of a Mangrove Ecosystem: A Radiotracer Study

The removal of ⁶⁵Zn from tidal water by underlaying sediment cores collected in a mangrove forest and a tidal creek that drains this forest in Sepetiba Bay (SE Brazil) was investigated. After 30-h experiments in laboratory microcosms, the ⁶⁵Zn half-removal times from tidal creek and mangrove forest sediments were 8.7?±?1.8 and 9.2?±?0.9 h respectively. Depth penetration of ⁶⁵Zn was mainly restricted to the upper 3 cm in mangrove forest cores, while detectable ⁶⁵Zn activities were found in all layers (0–7 cm depth) of tidal creek cores. An unexpected ⁶⁵Zn release back to the overlaying water was observed for one of the tidal creek experiments in the 12–18 h interval (corresponding to a return of 17% of the initial ⁶⁵Zn activity in overlaying water), suggesting a reversibility of the ⁶⁵Zn removal process (e.g., by adsorption) in tidal creek sediments. The results indicate that mangrove-vegetated sediments allowed a lower vertical mobility of Zn than observed in creek sediments and mangrove sediments appear to be less susceptible to a reversion in the process of zinc removal from overlaying water, suggesting a greater capacity to retain this metal near the water–sediment interface. This first radiotracer approach on the mangrove sediments removal of Zn from tidal waters supports earlier experimental studies employing stable Zn, contributing for a better understanding of the metal uptake kinetics by such sediments and suggesting that these sediments act as active sinks for trace metals.     

Trace Element Concentrations in Saltmarsh Soils Strongly Affected by Wastes from Metal Sulphide Mining Areas

Soil and water samples were analysed for trace metals and As in two watercourses and 14 sampling plots in a salt marsh polluted by mine wastes in SE Spain. Groundwater levels, soil pH and Eh were measured ‘in situ’ for a 12-month period in each sampling plot, and total calcium carbonate was also determined. Low concentrations of soluble metals (maximum Mn 1.089 mg L^?1 and maximum Zn 0.553 mg L^?1) were found in the watercourses. However, total metal contents were extremely high in the soils of a zone of the salt marsh (maximum 1,933 mg kg^?1 of Mn, 62,280 mg kg^?1 of Zn, 16,845 mg kg^?1 of Pb, 77 mg kg^?1 of Cd, 418 mg kg^?1 of Cu and 725 mg kg^?1 of As), and soluble metals in the pore water reached 38.7 mg L^?1 for Zn, 3.15 mg L^?1 for Pb, 48.0 mg L^?1 for Mn, 0.61 mg L^?1 for Cd and 0.29 mg L^?1 for As. Variable concentrations with depth indicate a possible re-mobilisation of the metals, which could be related to spatial and temporal variations of water table level, pH and Eh and to the presence of calcium carbonate. A tendency for the Eh to decrease in the warmest months and to increase in the coldest ones was found, especially, in plots that received water with a high content of dissolved organic carbon. Hence, the existence of nutrient effluent-enriched water may modify the physical–chemical conditions of the soil–water system and influence metal mobility.     

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.     

Trace metals in a tropical river environment-distribution

Distribution of trace metals in the Periyar river has been investigated in detail. The fluvial concentrations of trace metals increase in river water and decrease in sediments during the summer months due to solubilization and concentration by evaporation. The levels, especially of Zn and Cd which are industrial pollutants increase by a factor of 10 both in water and sediments at the industrial zone. The concentration of Cd in the river water approaches the WHO standards for safe limits in drinking water. Solubilization at the backwater zone under high salinity is identified as one of the major mechanisms of trace metal transport to the marine environment. River meandering is responsible for large scale deposition of suspended solids at the industrial zone during the monsoon period. The trace metals exhibit build-up in specific concentration in the suspended solids in proportion to their residence time.     

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.     

Potentially Toxic Trace Metals in Water and Lake-Bed Sediment of Panchpokhari,an Alpine Lake Series in the Central Himalayan Region of Nepal

This study assessed the level of potentially toxic trace metals (PTMs), seasonal variations, and their possible sources from the surface water and lake-bed sediment of Panchpokhari lake series, an alpine and glacial lake at 4160 m a.s.l. in Central Nepal. The lake series have five lakes, with Lake-1 larger than others. So, Lake-1 was investigated thoroughly during pre-monsoon and post-monsoon seasons. Sediment core was collected from the deepest basin of the Lake-1 during pre-monsoon. Most of the PTM concentrations were higher in the pre-monsoon season; however, Sc, Cr, Cu, Zn, As, and Ag were higher in the post-monsoon. This is an indication that the lake has been impacted either by natural or long-range transported atmospheric pollutants. Ti, Sb, and Ag had extremely high enrichment factor (EF) in waters, whereas Cd, Zn, and As had high EF in sediments indicating that these metals originated from anthropogenic sources. Furthermore, PTM concentrations in the sediment were in the increasing order of Hg < Cd < Ag < Mo < Sb < Sn < As < U < Sc < Co < Cs < Cu < Pb < Ni < Cr < V < Zn < Rb < Mn < Ti < Fe and showed that the upper layer (top 10 cm) of lake sediment has been receiving a higher load of PTMs in the recent period. he observed EF values also suggested that major sources of PTMs in the sediment were from crustal origin except for a few metals (Ti, V, Sb, and Ag) which were enriched anthropogenically due to long-range transport of atmospheric pollutants, deposited at the higher elevations. Nevertheless, the level of pollution in sediments was low as indicated both by EF and geo-accumulation index.     

Relationship Between pH and Stream Water Total Mercury Concentrations in Shenandoah National Park

The purpose of this study was to gather information on the spatial and temporal variation of stream water total mercury concentrations ([THg]) and to test the hypothesis that stream water [THg] increases as stream pH decreases in the Shenandoah National Park (SNP). We based our hypothesis on studies in lakes that found mercury methylation increases with decreasing pH, and studies in streams that found total mercury and other trace metal concentrations increase with decreasing pH. Stream water was collected at baseflow in SNP in April, July, and October 2005 and February 2006. Contrary to our hypothesis, stream water [THg] decreased with decreasing pH and acid neutralizing capacity. In SNP, stream pH and acid neutralizing capacity are strongly influenced by bedrock geology. We found that bedrock also influences stream water [THg]. Streams on basaltic bedrock had higher [THg] (0.648 ng L^?1?±?0.39) than streams on siliciclastic bedrock (0.301 ng L^?1?±?0.10) and streams on granitic bedrock (0.522 ng L^?1?±?0.06). The higher pH streams on basaltic bedrock had the highest [THg]. The variation in stream water [THg] occurred despite no known variation in wet deposition of mercury across the SNP. The findings of this study indicate that the SNP can be an important area for mercury research with significant variations in mercury concentrations across the park.     

Simultaneous Use of Trace Metals, 210Pb and 137Cs in Floodplain Sediments of a Lowland River as Indicators of Anthropogenic Impacts

This study focuses on the distribution of selected trace metals, ¹³⁷Cs and ²¹⁰Pb, in floodplain deposits of the lowland Warta River (southern Poland) downstream of Cz?stochowa, a large city with an iron smelter. The depth profiles of trace metal (Zn, Pb, Cu, Ni, Cd and Mn), ²¹⁰Pb and ¹³⁷Cs contents in floodplain sediments were used to derive deposition rates on the floodplain for the twentieth century. The applicability of particular chronometric tools is considered within the context of their mutual relationships and confirmed by the consistency of the results. Deposition rate estimates for the past 50 years based on the vertical patterns of trace metal concentrations, which were correlated with particular events in the development of the smelter, range from 0.4 cm·year^?1 in profiles situated in backswamps far from the channel to over 1.1 cm·year^?1 in profiles of the natural levee adjacent to the river. Deposition rates based on ²¹⁰Pb inventories in the profiles range from 0.08 to 0.66 g·cm^?2·year^?1, which corresponds to linear sedimentation rates of 0.10 to 0.91 cm·year^?1, respectively. Dating of characteristic levels associated with peak fallout of ¹³⁷Cs gives sediment accretion rates resembling those obtained from trace metals and ²¹⁰Pb. The period of the highest sediment accumulation rate could be related to the highest loads of effluent from the iron smelter and city of Cz?stochowa, which were substantially reduced after the construction of effluent treatment plant.     

Sediment denitrification in waterways in a rice-paddy-dominated watershed in eastern China

Purpose

Rice-paddy-dominated watersheds in eastern China are intensively cultivated, and lands with two crops receive as much as 550–600 kg?ha^–1?year^–1 of nitrogen (N), mainly through the addition of N-based fertilizers. However, stream N concentrations have been found to be relatively low. Waterways in the watersheds are assumed to be effective “sinks” for N, minimizing its downstream movement. We directly measured net sediment denitrification rates in three types of waterways (ponds, streams/rivers, and a reservoir) and determined the key factors that control net sediment denitrification. Such information is essential for evaluating the impact of the agricultural N cycle on the quality of surface water.

Materials and methods

The pond–stream–reservoir continuum was sampled every 2 months at nine sites in an agricultural watershed between November 2010 and December 2011. Net sediment N₂ fluxes/net sediment denitrification rates were determined by membrane inlet mass spectrometry and the N₂/Ar technique. A suite of parameters known to influence denitrification were also measured.

Results and discussion

Net denitrification rates ranged between 28.2?±?18.2 and 674.3?±?314.5 μmol N₂–N?m^–2?h^–1 for the streams, 23.7?±?23.9 and 121.2?±?38.7 μmol N₂–N?m^–2?h^–1 for the ponds, and 41.8?±?17.7 and 239.3?±?49.8 μmol N₂–N?m^–2?h^–1 for the reservoir. The mean net denitrification rate of the stream sites (173.2?±?248.4 μmol N₂–N?m^–2?h^–1) was significantly higher (p?<?0.001) than that of the pond sites (48.3?±?44.5 μmol N₂–N?m^–2?h^–1), and the three types of waterways all had significantly higher (p?<?0.01) mean net denitrification rates in summer than in other seasons. Linear regression and linear mixed effect model analysis showed that nitrate (NO₃ ^?–N) concentration in surface water was the primary controlling factor for net sediment denitrification, followed by water temperature. Using monitoring data on NO₃ ^?–N concentrations and temperature of the surface water of waterways and an established linear mixed effect model, total N removed through net sediment denitrification in the pond–stream–reservoir continuum was estimated at 46.8?±?24.0 t?year^–1 from July 2007 to June 2009, which was comparable with earlier estimates based on the mass balance method (34.3?±?12.7 t?year^–1), and accounted for 83.4 % of the total aquatic N. However, the total aquatic N was only 4.4 % of the total N input to the watershed, and thus most of the surplus N in the watershed was likely to be either denitrified or stored in soil.

Conclusions

High doses of N in a rice-paddy-dominated watershed did not lead to high stream N concentrations due to limited input of N into waterways and the high efficiency of waterways in removing N through denitrification.     

Diazinon Mitigation in Constructed Wetlands: Influence of Vegetation

In intensively cultivated areas, agriculture is a significant source of pesticides associated with storm runoff. When these pollutants enter aquatic receiving waters, they have potential to damage nearby aquatic ecosystems. Constructed wetlands are a best management practice (BMP) designed to help alleviate this potential problem. A constructed wetland system (180?×?30 m) comprised of a sediment retention basin and two treatment cells was used to determine fate and transport of a simulated storm runoff event containing the insecticide diazinon and suspended sediment. Wetland water, sediment, and plant samples were collected spatially and temporally over 55 d. Results indicated that 43% of the study’s measured diazinon mass was associated with plant material, while 23 and 34% were measured in sediment and water, respectively. Mean diazinon concentrations in water, sediment, and plants for the 55-d study were 18.1?±?4.5 μg/l, 26.0?±?8.0 μg/kg, and 97.8?±?10.7 μg/kg, respectively. Aqueous concentrations fluctuated in the wetlands between 51–86 μg/l for the first 4 h of the experiment; however, by 9 h, aqueous concentrations were approximately 16 μg/l. During the 55 d experiment, 0.3 m of rainfall contributed to fluctuations in diazinon concentrations. Results of this experiment can be used to model future design specifications for mitigation of diazinon and other pesticides.     

Relative Effect of Temperature and pH on Diel Cycling of Dissolved Trace Elements in Prickly Pear Creek,Montana

Diel (24 hr) cycles in dissolved metal and As concentrations have been documented in many northern Rocky Mountain streams in the U.S.A. The cause(s) of the cycles are unknown, although temperature- and pH-dependent sorption reactions have been cited as likely causes. A light/dark experiment was conducted to isolate temperature and pH as variables affecting diel metal cycles in Prickly Pear Creek, Montana. Light and dark chambers containing sediment and a strand of macrophyte were placed in the stream to simulate instream temperature oscillations. Photosynthesis-induced pH changes were allowed to proceed in the light chambers while photosynthesis was prevented in the dark chambers. Water samples were collected periodically for 22 hr in late July 2001 from all chambers and the stream. In the stream, dissolved Zn concentrations increased by 300% from late afternoon to early morning, while dissolved As concentrations exhibited the opposite pattern, increasing 33% between early morning and late afternoon. Zn and As concentrations in the light chambers showed similar, though less pronounced, diel variations. Conversely, Zn and As concentrations in the dark chambers had no obvious diel variation, indicating that light, or light-induced reactions, caused the variation. Temperature oscillations were nearly identical between light and dark chambers, strongly suggesting that temperature was not controlling the diel variations. As expected, pH was negatively correlated (P < 0.01) with dissolved Zn concentrations and positively correlated with dissolved As concentrations in both the light and dark chambers. From these experiments, photosynthesis-induced pH changes were determined to be the major cause of the diel dissolved Zn and As cycles in Prickly Pear Creek. Further research is necessary in other streams to verify that this finding is consistent among streams having large differences in trace-element concentrations and mineralogy of channel substrate.     

In-Stream Processing of Sediment-Associated Metals in Peatland Fluvial Systems

The interaction between fluvially transported, metal contaminated peat particulates and acidic waters draining peatland catchments has received limited attention. Potential in-stream processing of sediment-associated metals in acidic stream water was investigated in laboratory based mixing experiments, designed to represent conditions of fluvial sediment transport in a highly contaminated and severely eroding peatland catchment in the Peak District (UK). Over the initial 20 min of the first experiment, stream water Cr and Zn concentrations increased by at least an order-of-magnitude and remained elevated for the full duration (24 h) of the experiment. Stream water As, Mo, Pb, Ti and V concentrations increased between 43% (As) and 440% (V) over the first hour of the experiment. After 24 h most of the metals appeared to have reached equilibrium in the water column. Results of the second experiment revealed that when the concentration of metal contaminated peat particulates is increased, there is an associated increase in the stream water As, Cr, Mo, Pb, Ti, V and Zn concentrations. The experimental data suggest that As, Cr, Mo, Pb, Ti, V and Zn are liable to desorption from metal contaminated peat into acidic stream water. The solubilisation of contaminated peat particulates may also contribute to elevated stream water metal concentrations. The laboratory based approach used in this study may indicate that when there is erosion of metal contaminated peat into acidic fluvial systems there is a concomitant increase in dissolved metal levels, especially when suspended sediment concentrations are high. Further laboratory and field based experiments are required to evaluate the relative importance of physical and chemical processes in the interaction between contaminated peat particulates and stream water in peatland fluvial systems.     

History and Trends of Sediment Contamination by Heavy Metals Within and Close to a Marine Area of National Interest: The Ligurian Sea off Cogoleto-Stoppani (Genoa, Italy)

Due to its remarkable sediment pollution caused by past industrial activities, the Mediterranean coastal area facing the town of Cogoleto (near Genoa) has been declared of “national interest”. Seven sediment cores were analysed to provide information on history and trend of heavy metal inputs, with a particular focus on Cr. Grain-size compositions and ²¹⁰Pb chronologies account for a strong influence of terrigenous inputs near the coast and the mouth of the Lerone Creek (draining the industrial settlement), with sand contents and accumulation rates varying from 40.3% and 0.7 cm year^?1 near shore to 2.5% and 0.1 cm year^?1 offshore. Heavy metal concentrations are high, notably Cr and Ni, and to a lesser extent, Ag, Hg, Pb, Cu and Zn. Cr, that shows past values up to 3,642 µg g^?1, presents only minor recent decreases. In the area, it has both natural and anthropogenic sources and their relative contributions were distinguished on the basis of Cr/Ni ratios. These are 1–1.5 in soils and rocks of the Lerone Creek catchment area but reach very high values (up to 10) in marine sediments due to the anthropogenic contribution. The anthropogenic influence is higher near the creek mouth, gradually decreases offshore and is negligible at the most distal site (ca. 2.9 km from the coast).