Modeling copper partitioning in surface waters

Suspended particulate matter from the surface waters of the Susquehanna, Christina and Brandywine Rivers was collected by tangential flow filtration to study copper partitioning. Copper adsorption increased with an increase of suspended particles and decreased with low pH values or with an increase of dissolved organic matter. Effects of particulate organic matter on copper distribution between suspended particulate and solution phases were studied using modified aluminum oxide. An increase of particulate organic matter enhanced copper adsorption. Copper adsorption per mass of particulate organic carbon was similar for the different sources of suspended particles. A model, based on copper adsorption on particles and complexation with dissolved organic matter, was developed to assess copper partition coefficient as a function of the easily measurable water quality parameters: pH, alkalinity, dissolved organic carbon and particulate organic matter. The partitioning model was calibrated on pH edge data using suspended particles collected from the three rivers. The model was verified using partitioning data as a function of dissolved organic matter. The model adequately describes the system containing natural suspended solids collected from the surface waters.     

Mercury dynamics of a temperate forested wetland

Wetlands have been identified as important sites of mercury methylation in catchments, but the range of wetland types and their geographic distribution for which methylmercury fluxes are reported in the literature are limited. Linkages among wetland hydrology, total mercury and methylmercury concentrations and fluxes, and other water quality parameters were assessed in a temperate forested swamp in Southern Ontario, Canada. Two hydrogeomorphically distinct stream reaches within the wetland exhibited differences in wetland-stream hydrologic connectivity, which strongly influenced mercury dynamics. Total mercury flux from both reaches to the downstream was highest during flow conditions in which the wetland and stream were hydrologically connected. The wetland as a whole was a net sink for total mercury and a net source for methylmercury to the downstream system. Both total mercury and methylmercury concentrations were related to dissolved and particulate organic carbon in stream waters, but these relationships were dependent upon the sampling location and flow conditions. Throughout the wetland, methylmercury concentrations exhibited temporal relationships with sulfate concentrations. Further, despite short surface water residence times, periods of wetland and stream disconnect and high pH (approx. 8) in surface water, methylmercury fluxes from this wetland to the downstream were similar to those from more stagnant and acidic wetlands.     

Mercury and trace metal partitioning and fluxes in suburban Southwest Ohio watersheds

Many natural watersheds are increasingly affected by changes in land use associated with suburban sprawl and such alterations may influence concentrations, partitioning, and fluxes of toxic trace metals in fluvial ecosystems. We investigated the cycling of mercury (Hg), monomethylmercury, cadmium, copper, lead, nickel, and zinc in three watersheds at the urban fringe of Dayton, Ohio, over a 13-month period. Metal concentrations were related positively to discharge in each stream, with each metal having a high affinity for suspended particles and Hg also having a noticeable association with dissolved organic carbon. Although not observed for the other metals, levels of Hg in river water varied seasonally and among streams. Yields of Hg from two of the catchments were comparable to that predicted for runoff of atmospherically deposited Hg (∼25% of wet atmospheric flux), whereas the third watershed had a significantly greater annual flux associated with greater particle-specific and filtered water Hg concentrations, presumably from a point source. Fluxes of metals other than Hg were similar among each watershed and suggestive of a ubiquitous source, which could be either atmospheric deposition or weathering. Results of this study indicate that, with the exception of Hg being increased in one watershed, processes affecting metal partitioning and loadings are similar among southwest Ohio streams and comparable to other North American rivers that are equally or less impacted by urban development. Relative differences in land use, catchment area, and presence or absence of waste water treatment facilities had little or no detectable effect on most trace metal concentrations and fluxes. This suggests that suburban encroachment on agricultural and undeveloped lands has either similarly or not substantially impacted trace metal cycling in streams at the urban fringe of Dayton and, by extension, other comparable metropolitan areas.     

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.     

Behaviour of Hg species in a microtidal deltaic system: the Isonzo River mouth (northern Adriatic Sea)

Mercury species in the highly stratified water column of the Isonzo River mouth (northern Adriatic Sea) were investigated in February, May and August 2002 (low-normal fluvial discharge). Total, dissolved and particulate mercury (Hg) and methylmercury (MeHg) were measured and their concentrations were related to physico-chemical parameters in terms of temperature, salinity, turbidity, O(2) concentrations and total suspended matter (TSM) as well as particulate organic carbon (POC) content. Particulate Hg and MeHg are well correlated to medium-fine silty suspended sediment and organic matter, respectively. Desorption of Hg from particles in the brackish layer was observed. Due to the presence of a saltwedge, the lower river course seems to be a trap for Hg carried by fluvial waters. MeHg normally decreases approaching the sea but the local increase in the inner zone of the saltwedge could be related to methylation processes in the bottom water layer. Hg export is effective only during medium and high riverine flows acting as an important source of Hg into the northern Adriatic and the adjacent lagoon system.     

Concentration of mercury, methylmercury, cadmium, lead, arsenic, and selenium in the rain and stream water of two contrasting watersheds in western Maryland.

Weekly wet deposition and throughfall rain samples were collected in the Blacklick Run (BLK) and Herrington Creek Tributary (HCRT), two streams in western Maryland (MD). Samples were analyzed for total mercury (Hg), methylmercury (MMHg). arsenic (As), selenium (Se), cadmium (Cd), and Icad (Pb). Hg concentrations generally fell between 50 and 100 pM. comparable to concentrations in wet deposition measured at other MD sites. While Hg concentrations decreased with rainfall amount, a similar washout trend was not seen for MMHg. Cd, Pb, As, and Se concentrations were comparable overall to those measured in the region. Concentrations of Hg, Cd, and Pb in throughfall were similar between sites and equivalent or higher than wet deposition concentrations. As and Se concentrations were similar in throughfall at the two sites, though throughfall at BLK seemed to be punctuated with slightly higher concentrations of these two metals. Concentrations of Hg, MMHg, Cd, Pb, As, Se, and SPM were measured in monthly stream collections and compared with concentrations found in other MD rivers. In addition to the monthly collections, four storm events were sampled. These measurements demonstrate the importance of storm events in trace metal transport, especially for Hg, Pb and MMHg. For these metals, a strong correlation between metal and suspended particulate concentration was evident. Retention efficiencies of the watersheds for the metals were calculated for each watershed. Of all the metals, Hg is the most and As is the least strongly retained in the watershed.     

Levels of heavy metals in outdoor and indoor dusts in Muscat,Oman

The concentrations of lead, copper, nickel, zinc and chromium in outdoor and indoor dusts collected from different sites in Muscat, Oman, were determined by flame atomic absorption. Results showed a wide range of concentrations, the means in the outdoor dust being, 65?±?50, 124?±?316, 47?±?45, 930?±?666 and 64?±?26 mg kg^??1 for lead, zinc, copper, nickel and chromium, respectively. The 2001 Omani phasing out of leaded fuel resulted in low levels of lead in outdoor dust compared to those reported in the literature. Outstanding was the high nickel concentration in outdoor dust when compared to that in the literature, the reason being natural soil pollution due to the local geology of the northern parts of Oman. The concentrations of chromium, copper and zinc are lower than or comparable to these in other cities around the world. The results also showed that the industrial activities in Muscat do not contribute significantly to metal pollution in street dusts.

On the other hand, the mean concentrations of lead, zinc, copper, nickel and chromium in indoor dust were 108?±?65, 753?±?1162, 108?±?91, 130?±?125 and 34?±?14 mg kg^??1, respectively. In general, zinc and nickel levels are higher than those reported in the literature while lead, copper and chromium levels are lower or comparable.

When outdoor and indoor dusts were correlated, the ratios between indoor–outdoor mean concentrations revealed that lead, zinc, and copper were generated internally, while nickel and chromium were from external sources.     

Land inputs of trace metals, major elements, particulate organic carbon and suspended solids to an industrial coastal bay of the NE Atlantic

Rivers, streams and municipal and industrial effluents flowing into the Ferrol Ria (NW Spain) were analyzed for dissolved and particulate trace elements (Cd, Cu, Pb, Zn), particulate major elements (Al, Fe, Si), particulate organic carbon and nitrogen (POC and PON), and total suspended solids. Trace metal clean techniques were applied. Mean annual fluxes of these components were calculated. Dissolved trace metal concentrations in the major freshwater inputs were found to be within typical values for uncontaminated rivers: Cd: 0.020-0.035 nM; Cu: 11.7-19.2 nM; Pb: 0.40-0.71 nM and Zn: 18-54 nM. Two sources of suspended particulate matter (SPM) were observed: (i) a detrital SPM, which becomes more important at high river discharges, with metal concentrations tending to lithogenic values; (ii) an organic- and metal-rich SPM, which becomes dominant at low discharges. Municipal and industrial effluents in the northern shore, despite of constitute a minor freshwater contribution to the bay, were responsible for more than 50% of total inputs of Cu, Cd, Pb, Zn, POC and PON. The fluxes of trace metals obtained for the Ferrol Ria are in the range of other inhabited world semi-enclosed embayments.     

Mercury in the river mersey, its estuary and tributaries during 1973 and 1974

Mercury levels found in waters and suspended matter from 53 stations, occupied four times at 3-monthly intervals, showed that most mercury was associated with particulates but the amount varied during the year. In the polluted region between Warrington and Runcorn, where fresh-water and sea-water converge, >80% of the mercury was associated with the particulates. Dissolved mercury concentrations and the mercury load on particulate matter were always greater in freshwater than in tidal waters, except during a flood. A model of partitioning of mercury between particulate and dissolved phases is presented. The River Weaver and the Manchester Ship Canal were grossly polluted with mercury throughout that year due to a Castner-Kelner plant at Runcorn. Dredge spoils and water flow transport 17 (range 8–138) and 1.55 ± 65% tonnes yr⁻¹ respectively of mercury into Liverpool Bay.     

Removal of zeolite type a during primary sedimentation and its effect on metal removal

Using two pilot plants operated in parallel, treating settled sewage the removal of the detergent builder zeolite type A during primary sedimentation has been studied. With one zeolite free pilot plant acting as a control to the other it was also possible to determine the effect of zeolite on suspended solids and heavy metal removal over a range of hydraulic loadings. At both influent concentrations of zeolite studied (30 and 60 mg l⁻¹) zeolite removal was substantial under all conditions. No evidence of enhanced removal of suspended solids in the presence of zeolite was observed. Removals of lead, zinc, copper and chromium were slightly enhanced in some experiments. The observed improvements in metal removal appeared to be strongly influenced by the sewage matrix.     

Effects of chloride,sulfate and natural organic matter (NOM) on the accumulation and release of trace-level inorganic contaminants from corroding iron

This study examined effects of varying levels of anions (chloride and sulfate) and natural organic matter (NOM) on iron release from and accumulation of inorganic contaminants in corrosion scales formed on iron coupons exposed to drinking water. Changes of concentrations of sulfate and chloride were observed to affect iron release and, in lesser extent, the retention of representative inorganic contaminants (vanadium, chromium, nickel, copper, zinc, arsenic, cadmium, lead and uranium); but, effects of NOM were more pronounced. DOC concentration of 1 mg/L caused iron release to increase, with average soluble and total iron concentrations being four and two times, respectively, higher than those in the absence of NOM. In the presence of NOM, the retention of inorganic contaminants by corrosion scales was reduced. This was especially prominent for lead, vanadium, chromium and copper whose retention by the scales decreased from >80% in the absence of NOM to <30% in its presence. Some of the contaminants, notably copper, chromium, zinc and nickel retained on the surface of iron coupons in the presence of DOC largely retained their mobility and were released readily when ambient water chemistry changed. Vanadium, arsenic, cadmium, lead and uranium retained by the scales were largely unsusceptible to changes of NOM and chloride levels. Modeling indicated that the observed effects were associated with the formation of metal–NOM complexes and effects of NOM on the sorption of the inorganic contaminants on solid phases that are typical for iron corrosion in drinking water.     

The effect of heavy metals on laboratory populations of two polychaetes with comparisons to the water quality conditions and standards in Southern California marine waters

Polychaetous annelid assays were performed with laboratory inbred cultures of juvenile and adult Neanthes arenaceodentata and Capitella capitata to cadmium, chromium, copper, lead, mercury, and zinc in sea water. Data were presented as 96-h and 28-day LC₅₀ concentrations. Mercury and copper were the two most toxic with zinc and chromium generally the next most toxic followed by lead and cadmium. The adult stages of both species were more tolerant to these metals than the juveniles. Comparisons of these six metals present in the two large domestic sewage outfalls in Los Angeles County indicate that the amount of copper and zinc present in the effluent exceeds the 28-day LC₅₀ of these two polychaetes. The results were compared to the water quality standards for discharges in the State of California.     

Ingestion risks of metals in groundwater based on TIN model and dose-response assessment — A case study in the Xiangjiang watershed, central-south China

Groundwater samples were collected in the Xiangjiang watershed in China from 2002 to 2008 to analyze concentrations of arsenic, cadmium, chromium, copper, iron, lead, mercury, manganese, and zinc. Spatial and seasonal trends of metal concentrations were then discussed. Combined with geostatistics, an ingestion risk assessment of metals in groundwater was performed using the dose-response assessment method and the triangulated irregular network (TIN) model. Arsenic concentration in groundwater had a larger variation from year to year, while the variations of other metal concentrations were minor. Meanwhile, As concentrations in groundwater over the period of 2002-2004 were significantly higher than that over the period of 2005-2007, indicating the improvement of groundwater quality within the later year. The hazard index (HI) in 2002 was also significantly higher than that in 2005, 2006, 2007 and 2008. Moreover, more than 80% of the study area recorded an HI of more than 1.0 for children, suggesting that some people will experience deleterious health effects from drinking groundwater in the Xiangjiang watershed. Arsenic and manganese were the largest contributors to human health risks (HHRs). This study highlights the value of long-term health risk evaluation and the importance of geographic information system (GIS) technologies in the assessment of watershed-scale human health risk.     

Metal loadings and removal at a municipal activated sludge plant

Influent total and dissolved concentrations of cadmium, chromium, copper, nickel and zinc to the Edmonton Gold Bar Wastewater Treatment Plant were measured at hourly intervals for several days. Metal concentrations were generally higher than in other large western Canadian cities and exhibited distinct diurnal variations. With the exceptions of nickel and zinc, the metals existed largely in the particulate phase. Samples collected from various points throughout the plant suggested that removal efficiencies for cadmium, chromium and copper were high and those for nickel and zinc were variable and generally low. Metal concentrations in the final effluent did not generally exceed the maximum levels allowed for Canadian drinking waters.     

Particle size distribution and atmospheric metals measurements in a rural area in the South Eastern USA

Atmospheric particle mass concentrations were measured at a site adjacent to Lake Hartwell, GA, during six dry sampling events in February-March 2003. The overall average PM2.5 mass concentration was 9.5 microg/m3 and the overall average total suspended particles mass concentration was 19.1 microg/m3. Particulate matter was collected on a deposition plate mounted onto a specially designed wind vane and was subsequently analyzed to determine the particle size distribution. The average geometric particle diameter was found to be 2.8 microm. Particulate matter collected was found to be closely approximately at log-normal distribution, with a count median diameter of 1.5 mum and a geometric standard deviation of 1.8. Individual metal concentrations present in airborne particulate matter were determined for cadmium, chromium, copper, iron, lead, manganese, nickel, and zinc using inductively coupled plasma-mass spectrometry analysis of samples collected on Teflon filters. Ambient metal concentrations were found to range from 0.8 ng/m3 for cadmium to 512 ng/m3 for iron. The dry deposition flux of metals was estimated to be in the range of 0.17 mg/(m2 year) for cadmium to 102 mg/(m2 year) for iron. More samples need to be collected and analyzed, both temporally and spatially, in order to establish atmospheric metals fluxes onto surfaces.     

Export of mercury downstream from reservoirs

Environmental effects monitoring at the La Grande hydroelectric complex (Québec, Canada) revealed important increases in mercury levels in fish caught downstream from reservoirs. A study was carried out in 1997 immediately below the Caniapiscau Reservoir to identify by which components mercury is transported downstream from reservoirs and to assess the amount of mercury being exported. Stomach contents of lake whitefish (Coregonus clupeaformis) captured immediately below the Caniapiscau Reservoir were examined to determine which components transfer mercury from lower trophic levels to fish. The analyses of water samples and drifting organisms collected below the reservoir indicate that the dissolved fraction (< 0.45 microm) and the suspended particulate matter (0.45-50 microm) are the major components by which methylmercury is transferred downstream of reservoirs, accounting for 64 and 33%, respectively, of the total amounts exported. Drifting organisms such as plant debris, benthic invertebrates, fish, phytoplankton and zooplankton are much less important pathways for mercury export because of their very low biomass per water volume coming out of the generating station, as opposed to the high biomass of suspended particulate matter. However, zooplankton is the major component by which methylmercury is directly transferred to non-piscivorous fish downstream.     

Composition of particulate and dissolved organic matter in a disturbed watershed of southeast Brazil (Piracicaba River basin)

The elemental and isotopic composition of particulate and dissolved organic matter was investigated in the Piracicaba River basin, S?o Paulo State, Brazil. Comparison of riverine organic matter from the Piracicaba River basin, a region where rivers and streams receive urban sewage and industrial effluents, with data reported for the pristine Amazon system revealed significant differences associated with anthropogenic impacts. One important difference was N enrichment in the particulate organic material of the Piracicaba basin rivers, due to (a) urban and industrial effluents, and (b) enhanced phytoplankton growth, which results from the combination of nutrient enrichment and damming of sections of the rivers. Radiocarbon concentrations were overall more depleted (older 14C age) in the Piracicaba basin rivers than in the Amazon, which may reflect the importance of soil erosion in the former. Analyses of stable and radioactive carbon isotopes and lignin-derived compounds indicated that coarse particulate organic material is composed of a mixture of soil particles and degraded organic matter from C3 and C4 vascular plants. Fine particulate organic material was composed mainly of soil particles and phytoplankton cell remains, the latter especially during low water. Ultrafiltered dissolved organic matter was the most degraded fraction according to its lignin oxidation products, and showed the greatest influence of C4 plant sources.     

Partitioning of marine antifoulants in the marine environment

The partitioning behaviour of the organic biocides, Irgarol 1051 and diuron and two inorganic biocides (copper and zinc) was investigated using six sediments of differing physico-chemical properties collected from unimpacted sites along the south coast of England. The kinetics of sorption and equilibrium partitioning between the sediments and seawater were investigated over a period of 20 days. Resulting organic carbon/water partition coefficients (log Koc) were related to suspended sediment concentration and ranged from 2.28 to 5.20 for diuron; and from 2.41 to 4.89 for Irgarol 1051. Sediment/water partition coefficients (log Kp) for copper and zinc varied from 2.46 to 5.08 l/kg and from 2.49 to 4.97 l/kg, respectively. Kinetic data indicated that there were significant interactions between the dissolved and particulate phases at the start of the experiments, just after mixing. This is thought to be a result of redistribution of organic carbon between the two phases.     

Methylmercury in rivers draining cultivated watersheds

Total mercury (THg) concentrations in streams draining cultivated watersheds in Minnesota, USA are strongly correlated with total suspended sediment (TSS) concentrations, varying widely in response to precipitation-driven inputs of soil-derived suspended sediments. Methylmercury (MeHg) concentrations in these waterways have not been studied, and little is known about mercury uptake mechanisms in resident fish populations. To begin to identify factors influencing MeHg concentrations and loadings in these streams, we measured THg and MeHg concentrations in unfiltered whole water samples from the Minnesota River and two of its major tributaries, the Blue Earth and Le Sueur Rivers. Land use in the watersheds of these rivers is over 90% row-crop agriculture, and extensive artificial drainage systems deliver runoff and associated solids quickly to local streams and rivers. THg concentrations were elevated (>10 ng/l) during much of Spring 2000 and part of the summer when runoff from precipitation events increased stream discharge and carried soil materials into the streams. Reduced precipitation resulted in low flow conditions from August through October, and THg concentrations decreased to <4.0 ng/l in all three rivers. MeHg concentrations in the Le Sueur River ranged from 0.07 to 0.42 ng/l between June and December. Higher MeHg concentrations (>0.2 ng/l) were measured during summer months when THg and TSS concentrations were high after precipitation events. Elevated MeHg concentrations were also observed in late October after leaf litter inputs. Conditions on the Blue Earth River were different, with elevated MeHg concentrations (>0.5 ng/l) observed during low flow in August and September. These higher concentrations coincided with a period of enhanced microbial growth stimulated by high late-summer temperatures. A late-October increase in MeHg concentration attributed to leaf litter inputs was also observed in this river. MeHg concentration trends in the Minnesota River were similar to those in the Blue Earth River. Indicators of biological productivity (chlorophyll a, volatile suspended solids, and total Kjeldahl nitrogen) were higher in the Blue Earth and Minnesota Rivers compared to the Le Sueur River, which may signal a connection between higher biological activity and increased MeHg concentrations.     

Mercury contaminations from historic mining to water, soil and vegetation in Lanmuchang, Guizhou, southwestern China

Concentrations of total mercury and methylmercury (MeHg) were measured in soil and vegetation samples collected from a small area with a long history of Hg-mining. Hg distributions were determined in stream-waters during two sampling periods. Total Hg concentrations in soil and vegetation samples were highly elevated ranging from 0.41 to 610 mg kg(-1) and from 0.02 to 55 mg kg(-1), respectively. MeHg concentrations varied from 0.41 to 8.8 microg kg(-1) in soil samples and from 0.65 to 5.5 microg kg(-1) in vegetations. The concentrations of total Hg in stream waters varied from 55.0 to 7020 ng L(-1) in the flood-flow regime and from 24.8 to 679 ng L(-1) in the base-flow regime, respectively. Average dissolved Hg concentration was 15.7 ng L(-1) in the wet season and 21.0 ng L(-1) in the dry season. However, particulate Hg was typically >70% of total Hg in the flood-flow regime. Higher concentrations of particulate Hg primarily originated from summer floods were the major pathway of Hg transportation, which were evidenced by the positive correlation between particulate Hg and total suspended solids (TSS). The contaminated soils and distribution patterns of Hg in the stream-waters may serve as an important source of Hg to the local environment in the study area.