Mercury concentrations in water from an unconfined aquifer system, New Jersey coastal plain

Concentrations of total mercury (Hg) from 2 microg/L (the USEPA maximum contaminant level) to 72 microg/L in water from about 600 domestic wells in residential parts of eight counties in southern New Jersey have been reported by State and county agencies. The wells draw water from the areally extensive (7770 km(2)) unconfined Kirkwood-Cohansey aquifer system, in which background concentrations of Hg are about 0.01 microg/L or less. Hg is present in most aquifer materials at concentrations <50 microg/kg, but is at 100--150 microg/kg in undisturbed surficial soils. No point sources of contamination to the affected areas have been conclusively identified. To determine whether high levels of Hg in ground water are related to a particular land use and (or) water chemistry, water samples from 105 wells that tap the aquifer system were collected by the United States Geological Survey. These included randomly selected domestic wells, domestic and observation wells in selected land uses, and sets of clustered observation wells--including two sets that are downgradient from residential areas with Hg-contaminated ground water. Hg concentrations in filtered samples (Hg(f)) were at or near background levels in water from most wells, but ranged from 0.1 to 3.8 microg/L in water from nearly 20% of wells. Hg(f) concentrations from 0.0001 to 0.1 microg/L correlated significantly and positively with concentrations of other constituents associated with anthropogenic inputs (Ca, Cl, Na, and NO(3)) and with dissolved organic carbon. Hg(f) concentrations >0.1 microg/L did not correlate significantly with concentrations of the inorganic constituents. Hg(f) concentrations near or exceeding 2 microg/L were found only in water from wells in areas with residential land use, but concentrations were at background levels in most water samples from undeveloped land. The spatial distribution of Hg-contaminated ground water appears to be locally and regionally heterogeneous; no extensive plumes of Hg contamination have yet been identified.     

Occurrence of antibiotics in hospital, residential, and dairy effluent, municipal wastewater, and the Rio Grande in New Mexico

This study had three objectives: 1) determine occurrence of antibiotics in effluent from hospitals, residential facilities, and dairies, and in municipal wastewater 2) determine antibiotic removal at a large wastewater treatment plant (WWTP) in Albuquerque, NM, and 3) determine concentrations of antibiotics in the Rio Grande, which receives wastewater from the Albuquerque WWTP. Twenty-three samples of wastewater and 3 samples of Rio Grande water were analyzed for the presence of 11 antibiotics. Fifty-eight percent of samples had at least one antibiotic present while 25% had three or more. Hospital effluent had detections of sulfamethoxazole, trimethoprim, ciprofloxacin, ofloxacin, lincomycin, and penicillin G, with 4 of 5 hospital samples having at least one antibiotic detected and 3 having four or more. At the residential sampling sites, ofloxacin was found in effluent from assisted living and retirement facilities, while the student dormitory had no detects. Only lincomycin was detected in dairy effluent (in 2 of 8 samples, at 700 and 6600 ng/L). Municipal wastewater had detections of sulfamethoxazole, trimethoprim, ciprofloxacin, and ofloxacin, with 4 of 6 samples having at least one antibiotic present and 3 having 3 or more. The relatively high concentrations (up to 35,500 ng/L) of ofloxacin found in hospital and residential effluent may be of concern due to potential genotoxic effects and development of antibiotic resistance. At the Albuquerque WWTP, both raw wastewater and treated effluent had detections of sulfamethoxazole, trimethoprim, and ofloxacin, at concentrations ranging from 110 to 470 ng/L. However, concentrations in treated effluent were reduced by 20% to 77%. No antibiotics were detected in the Rio Grande upstream of the Albuquerque WWTP discharge, and only one antibiotic, sulfamethoxazole, was detected in the Rio Grande (300 ng/L) below the WWTP.     

Impact of geochemical stressors on shallow groundwater quality

Groundwater monitoring wells (about 70 wells) were extensively installed in 28 sites surrounding Lake Texoma, located on the border of Oklahoma and Texas, to assess the impact of geochemical stressors to shallow groundwater quality. The monitoring wells were classified into three groups (residential area, agricultural area, and oil field area) depending on their land uses. During a 2-year period from 1999 to 2001 the monitoring wells were sampled every 3 months on a seasonal basis. Water quality assay consisted of 25 parameters including field parameters, nutrients, major ions, and trace elements. Occurrence and level of inorganics in groundwater samples were related to the land use and temporal change. Groundwater of the agricultural area showed lower levels of ferrous iron and nitrate than the residential area. The summer season data revealed more distinct differences in inorganic profiles of the two land use groundwater samples. There is a possible trend that nitrate concentrations in groundwater increased as the proportions of cultivated area increased. Water-soluble ferrous iron occurred primarily in water samples with a low dissolved oxygen concentration and/or a negative redox potential. The presence of brine waste in shallow groundwater was detected by chloride and conductivity in oil field area. Dissolved trace metals and volatile organic carbons were not in a form of concentration to be stressors. This study showed that the quality of shallow ground water could be related to regional geochemical stressors surrounding the lake.     

Concentrations of lead and mercury in multimedia samples from homes near the former Clark Air Base, Philippines

We measured lead and mercury in samples collected from 31 homes in communities near the former Clark Air Base, Philippines during May and October 2002. Sample media included water used for drinking and cooking, house dust and entryway soil. Composite samples of 15 food items purchased at local markets were also collected. Samples were analyzed for total lead (Pb) and total mercury (Hg) to evaluate the relative importance of each media to residential exposure concentrations in the community adjacent to Clark (Community A) versus a control community 5 km away (Community B). In general, we measured low (e.g. background) to undetectable levels of the target analytes in all media sampled with two important exceptions. First, the Hg concentrations we measured in canned mackerel composites, which were within the range reported for mackerel from other locations worldwide, may pose a risk to pregnant women who are frequent consumers (e.g. one or more cans per day). Second, we measured Pb above the USEPA residential screening concentration (400 mug/g) in dust and soil from two homes, illustrating the need for periodic residential lead monitoring in these and other communities in the Philippines. We found no significant difference between Communities A and B with respect to Pb and Hg concentrations in water or food, although we were not able to detect very low levels of Pb in most of the foods we sampled because of trace Pb contamination added during sample homogenization. Although the Pb levels we measured in dust and soil from Community A homes were higher on average than Community B homes, the levels in both communities were low (e.g. background) thus we did not investigate the difference further. To our knowledge, these are the first reported measurements of Pb in house dust in the Philippines. The concentrations of Pb we measured in house dust were significantly higher than those in entryway soil from both communities, adding empirical support to the assertion that yard soil should not be considered a proxy for house dust in exposure studies in the Philippines or elsewhere.     

Effects of time and point-of-use devices on arsenic levels in Southeastern Michigan drinking water, USA

Health effects associated with chronic, low-level exposures to arsenic in drinking water (<100 microg/L) remain unclear, in part due to uncertainties in assessing exposure. Drinking water concentrations have been used to assess past exposure to arsenic in epidemiological studies, under the assumption that a single measurement can be used to estimate historical exposure. This study aims to better understand (1) temporal variability in arsenic concentrations in drinking water and (2) the impact of point-of-use (POU) treatment devices on arsenic exposure measurements, and on reliability of the exposure measurement for population-level studies. Multiple drinking water samples were collected at two points in time (an average of fourteen months apart) for 261 individuals enrolled in a case-control study of arsenic exposure and bladder cancer in Michigan. Sources of drinking water included private wells (n = 221), public water supplies (n = 33), and bottled water (n = 7); mean arsenic concentration was highest in private wells (7.28 microg/L) and lowest in bottled water samples (0.28 microg/L). Arsenic concentrations in primary drinking water samples were highly correlated (r = 0.88, p < 0.0001, n = 196), with 3% of the water sources exceeding the United States Environmental Protection Agency's Maximum Contaminant Level (MCL) in one sample but not in the other sample. Measurement reproducibility did not vary by type of POU device (e.g., softener, filter, reverse osmosis system). Arsenic concentrations did differ, however, between samples treated with POU devices and untreated samples taken on the same day. Substantial differences in arsenic concentrations were consistently observed for reverse osmosis systems; other POU devices had variable effects on arsenic concentrations. These results indicate that while a single residential arsenic measurement may be used to represent exposure in this region, researchers must obtain information on changes in water source and POU treatment devices to better characterize population exposures over time.     

Factors affecting enhanced mercury bioaccumulation in inland lakes of Isle Royale National Park,USA

We investigated factors causing mercury (Hg) concentrations in northern pike to exceed the consumption advisory level (>500 ng/g) in some inland lakes of Isle Royale National Park. Using Hg-clean techniques, we collected water, zooplankton, macro invertebrates, and fishes in 1998 and 1999 from one advisory lake, Sargent Lake, for analysis of total mercury (Hg(T)) and methylmercury (MeHg). For comparison, samples were also collected from a non-advisory lake, Lake Richie. Concentrations of Hg(T) in northern pike were significantly higher in Sargent Lake (P<0.01). Counter to expectations, mean concentrations of both Hg(T) and MeHg in open water samples were slightly higher in Lake Richie. However, zooplankton in Sargent Lake contained higher average concentrations of Hg(T) and MeHg than in Lake Richie. Mercury concentrations in macro invertebrates were similar between lakes, but different between taxa. The two lakes exhibited similar Hg(T) concentrations in age-1 yellow perch and adult perch but concentrations in large adult perch (>160 mm) in Sargent Lake were twice the concentrations in Lake Richie. Analysis of stable isotopes (delta(13)C and delta(15)N) in biota showed that pike from the two lakes are positioned at the same trophic level (4.2 and 4.3), but that the food web is more pelagic-based in Sargent and benthic-based in Richie. Factors causing concentrations in large pike to be higher in Sargent Lake may include higher bioavailability of methylmercury and a food web that enhances bioaccumulation.     

Identifizierung der Eintragsquellen von Antibiotika in das Grundwasser viehstarker Regionen

Only few sulfonamide antibiotics were detected in near-surface groundwater in areas with a high stocking rate in northwestern Germany. Intensive sampling with a high resolution in time and space was applied in order to illuminate the findings. As some pharmaceuticals can be of both human and animal origin, they may enter the environment via application of manure/digestate to arable land or via domestic waste water. In addition to existing monitoring wells, non-permanent wells were sampled to obtain information regarding pathways into the ground water. Interviews with farmers and chemical analyses show that application of manure leads to low concentrations (<100 ng/l) of Sulfadimidin and Sulfadiazin in most of the investigated samples. Sulfamethoxazol was found above 100 ng/l and likely originated from sewage of nearby small scale wastewater treatment plants. Sulfamethoxazole and its main metabolite could be detected within the plants; additionally, the sewage tracer acesulfam-K was detected in the groundwater.     

Changes in sample collection and analytical techniques and effects on retrospective comparability of low-level concentrations of trace elements in ground water

Ground-water sampling techniques were modified to reduce random low-level contamination during collection of filtered water samples for determination of trace-element concentrations. The modified sampling techniques were first used in New Jersey by the US Geological Survey in 1994 along with inductively coupled plasma-mass spectrometry (ICP-MS) analysis to determine the concentrations of 18 trace elements at the one microgram-per-liter (microg/L) level in the oxic water of the unconfined sand and gravel Kirkwood-Cohansey aquifer system. The revised technique tested included a combination of the following: collection of samples (1) with flow rates of about 2 L per minute, (2) through acid-washed single-use disposable tubing and (3) a single-use disposable 0.45-microm pore size capsule filter, (4) contained within portable glove boxes, (5) in a dedicated clean sampling van, (6) only after turbidity stabilized at values less than 2 nephelometric turbidity units (NTU), when possible. Quality-assurance data, obtained from equipment blanks and split samples, indicated that trace element concentrations, with the exception of iron, chromium, aluminum, and zinc, measured in the samples collected in 1994 were not subject to random contamination at 1 microg/L. Results from samples collected in 1994 were compared to those from samples collected in 1991 from the same 12 PVC-cased observation wells using the available sampling and analytical techniques at that time. Concentrations of copper, lead, manganese and zinc were statistically significantly lower in samples collected in 1994 than in 1991. Sampling techniques used in 1994 likely provided trace-element data that represented concentrations in the aquifer with less bias than data from 1991 when samples were collected without the same degree of attention to sample handling.     

Pharmaceuticals and personal care products (PPCPs) in surface and treated waters of Louisiana,USA and Ontario,Canada

A newly developed analytical method was used to measure concentrations of nine pharmaceuticals and personal care products (PPCPs) in samples from two surface water bodies, a sewage treatment plant effluent and various stages of a drinking water treatment plant in Louisiana, USA, and from one surface water body, a drinking water treatment plant and a pilot plant in Ontario, Canada. The analytical method provides for simultaneous extraction and quantification of the following broad range of PPCPs and endocrine-disrupting chemicals: naproxen; ibuprofen; estrone; 17beta-estradiol; bisphenol A; clorophene; triclosan; fluoxetine; and clofibric acid. Naproxen was detected in Louisiana sewage treatment plant effluent at 81-106 ng/l and Louisiana and Ontario surface waters at 22-107 ng/l. Triclosan was detected in Louisiana sewage treatment plant effluent at 10-21 ng/l. Of the three surface waters sampled, clofibric acid was detected in Detroit River water at 103 ng/l, but not in Mississippi River or Lake Pontchartrain waters. None of the other target analytes were detected above their method detection limits. Based on results at various stages of treatment, conventional drinking-water treatment processes (coagulation, flocculation and sedimentation) plus continuous addition of powdered activated carbon at a dosage of 2 mg/l did not remove naproxen from Mississippi River waters. However, chlorination, ozonation and dual media filtration processes reduced the concentration of naproxen below detection in Mississippi River and Detroit River waters and reduced clofibric acid in Detroit River waters. Results of this study demonstrate that existing water treatment technologies can effectively remove certain PPCPs. In addition, our study demonstrates the importance of obtaining data on removal mechanisms and byproducts associated with PPCPs and other endocrine-disrupting chemicals in drinking water and sewage treatment processes.     

Fate of trace organics during rapid infiltration of primary wastewater at Fort Devens, Massachusetts

Transport and fate of trace organics were studied during rapid infiltration of primary wastewater at a land application facility in Fort Devens, Massachusetts. A preliminary sampling trip was made to compare trace organic concentrations in the infiltrating wastewater and in ground water samples from three monitoring wells around the site. Trace organic concentrations were reduced by the rapid infiltration process. However, significant concentrations of specific compounds could be detected in ground water down-gradient of the site.Therefore, a field study was undertaken to determine the primary region where trace organics were removed in the system. Teflon monitoring wells were installed at a depth of 1.2 m in one of the basins at the site prior to flooding. Flooding was initiated and samples of the raw wastewater, the wastewater entering the basin, the infiltrate at 1.2-m depth and the ground water down-gradient of the site were analyzed for six compounds selected for the study.Results from replicate samples during the 6-day flooding period demonstrated that most of the removal for the six compounds occurred in the top meter of the soil, although concentrations of each compound increased substantially in the basin infiltrate from two of the sample points after the fourth day of flooding. No removal of p-dichlorobenzene, p-(I,1,3,3-tetramethylbutyl)phenol and 2-(methylthio)benzothiazole was apparent in the aquifer itself, as indicated by relatively high concentrations of these compounds in the contaminated monitoring well down-gradient of the site.These data indicate that trace organic concentrations in primary effluent can be reduced by rapid infiltration and that most of the removal occurs in the top meter of the soil during the early phase of the flooding cycle. This removal capability can rapidly diminish, however, and result in ground water contamination by trace organics above background levels.     

Mercury distribution and speciation in Lake Balaton, Hungary

The distribution and speciation of mercury in air, rain, lake water, sediment, and zooplankton in Lake Balaton (Hungary) were investigated between 1999 and 2002. In air, total gaseous mercury (TGM) ranged from 0.4 to 5.9 ng m(-3) and particulate phase mercury (PPM) from 0.01 to 0.39 ng m(-3). Higher concentrations of both TGM and PPM occurred during daytime. Higher concentrations of PPM occurred in winter. In rain and snow, total mercury ranged from 10.8 to 36.7 ng L(-1) in summer but levels up to 191 ng L(-1) in winter. Monomethylmercury (MMHg) concentrations ranged from 0.09 to 1.26 ng L(-1) and showed no seasonal variations. Total Hg in the unfiltered lake water varied spatially, with concentrations ranging from 1.4 to 6.5 ng L(-1). Approximately 70% of the total Hg is dissolved. MMHg levels ranged from 0.08 to 0.44 ng L(-1) as total and from 0.05 to 0.37 ng L(-1) in the dissolved form. Lower Hg concentrations in the water column occurred in winter. In suspended particulate matter and in sediment, total mercury ranged from 9 to 160 ng g(-1) dw, and MMHg ranged from 0.07 to 0.84 ng g(-1) dw. In zooplankton, an average mercury level of 31.0+/-6.8 ng g(-1) dw occurred, with MMHg accounting for approximately 17%. In sediments, suspended-matter- and zooplankton-high Hg and MMHg levels occurred at the mouth of the River Zala, but, in the lake, higher concentrations occurred on the Northern side, and an increasing trend from north-west to north-east was observed. In general, regarding Hg, Lake Balaton can be considered as a relatively uncontaminated site. The high-pH and well-oxygenated water as well as the low organic matter content of the sediment does not favour the methylation of Hg. In addition, bioconcentration and bioaccumulation factors are relatively low compared to other aquatic systems.     

Distribution, speciation, and transport of mercury in stream-sediment, stream-water, and fish collected near abandoned mercury mines in southwestern Alaska, USA

Concentrations of total Hg, Hg (II), and methylmercury were measured in stream-sediment, stream-water, and fish collected downstream from abandoned mercury mines in southwestern Alaska to evaluate environmental effects to surrounding ecosystems. These mines are found in a broad belt covering several tens of thousands of square kilometers, primarily in the Kuskokwim River basin. Mercury ore is dominantly cinnabar (HgS), but elemental mercury (Hg degrees) is present in ore at one mine and near retorts and in streams at several mine sites. Approximately 1400 t of mercury have been produced from the region, which is approximately 99% of all mercury produced from Alaska. These mines are not presently operating because of low prices and low demand for mercury. Stream-sediment samples collected downstream from the mines contain as much as 5500 microg/g Hg. Such high Hg concentrations are related to the abundance of cinnabar, which is highly resistant to physical and chemical weathering, and is visible in streams below mine sites. Although total Hg concentrations in the stream-sediment samples collected near mines are high, Hg speciation data indicate that concentrations of Hg (II) are generally less than 5%, and methylmercury concentrations are less than 1% of the total Hg. Stream waters below the mines are neutral to slightly alkaline (pH 6.8-8.4), which is a result of the insolubility of cinnabar and the lack of acid-generating minerals such as pyrite in the deposits. Unfiltered stream-water samples collected below the mines generally contain 500-2500 ng/l Hg; whereas, corresponding stream-water samples filtered through a 0.45-microm membrane contain less than 50 ng/l Hg. These stream-water results indicate that most of the Hg transported downstream from the mines is as finely-suspended material rather than dissolved Hg. Mercury speciation data show that concentrations of Hg (II) and methylmercury in stream-water samples are typically less than 22 ng/l, and generally less than 5% of the total Hg. Muscle samples of fish collected downstream from mines contain as much as 620 ng/g Hg (wet wt.), of which 90-100% is methylmercury. Although these Hg concentrations are several times higher than that in fish collected from regional baseline sites, the concentration of Hg in fish is below the 1000 ng/g action level for edible fish established by the US Food and Drug Administration (FDA). Salmon contain less than 100 ng/g Hg, which are among the lowest Hg contents observed for fish in the study, and well below the FDA action level.     

Microbial transformations of arsenic: mobilization from glauconitic sediments to water

In the Inner Coastal Plain of New Jersey, arsenic (As) is released from glauconitic sediment to carbon- and nutrient-rich shallow groundwater. This As-rich groundwater discharges to a major area stream. We hypothesize that microbes play an active role in the mobilization of As from glauconitic subsurface sediments into groundwater in the Inner Coastal Plain of New Jersey. We have examined the potential impact of microbial activity on the mobilization of arsenic from subsurface sediments into the groundwater at a site on Crosswicks Creek in southern New Jersey. The As contents of sediments 33-90 cm below the streambed were found to range from 15 to 26.4 mg/kg, with siderite forming at depth. Groundwater beneath the streambed contains As at concentrations up to 89 μg/L. Microcosms developed from site sediments released 23 μg/L of As, and active microbial reduction of As(V) was observed in microcosms developed from site groundwater. DNA extracted from site sediments was amplified with primers for the 16S rRNA gene and the arsenate respiratory reductase gene, arrA, and indicated the presence of a diverse anaerobic microbial community, as well as the presence of potential arsenic-reducing bacteria. In addition, high iron (Fe) concentrations in groundwater and the presence of iron-reducing microbial genera suggests that Fe reduction in minerals may provide an additional mechanism for release of associated As, while arsenic-reducing microorganisms may serve to enhance the mobility of As in groundwater at this site.     

Atmospheric mercury speciation in Yellowstone National Park

Atmospheric concentrations of elemental mercury (Hg(0)), reactive gaseous Hg (RGM), and particulate Hg (pHg) concentrations were measured in Yellowstone National Park (YNP), U.S.A. using high resolution, real time atmospheric mercury analyzers (Tekran 2537A, 1130, and 1135). A survey of Hg(0) concentrations at various locations within YNP showed that concentrations generally reflect global background concentrations of 1.5-2.0 ng m(-3), but a few specific locations associated with concentrated geothermal activity showed distinctly elevated Hg(0) concentrations (about 9.0 ng m(-3)). At the site of intensive study located centrally in YNP (Canyon Village), Hg(0) concentrations did not exceed 2.5 ng m(-3); concentrations of RGM were generally below detection limits of 0.88 pg m(-3) and never exceeded 5 pg m(-3). Concentrations of pHg ranged from below detection limits to close to 30 pg m(-3). RGM and pHg concentrations were not correlated with any criteria gases (SO(2), NO(x), O(3)); however pHg was weakly correlated with the concentration of atmospheric particles. We investigated three likely sources of Hg at the intensive monitoring site: numerous geothermal features scattered throughout YNP, re-suspended soils, and wildfires near or in YNP. We examined relationships between the chemical properties of aerosols (as measured using real time, single particle mass spectrometry; aerosol time-of-flight mass spectrometer; ATOFMS) and concentrations of atmospheric pHg. Based on the presence of particles with distinct chemical signatures of the wildfires, and the absence of signatures associated with the other sources, we concluded that wildfires in the park were the main source of aerosols and associated pHg to our sampling site.     

Occurrence and removal of N-nitrosamines in wastewater treatment plants

The presence of nitrosamines in wastewater might pose a risk to water resources even in countries where chlorination or chloramination are hardly used for water disinfection. We studied the variation of concentrations and removal efficiencies of eight N-nitrosamines among 21 full-scale sewage treatment plants (STPs) in Switzerland and temporal variations at one of these plants. N-nitrosodimethylamine (NDMA) was the predominant compound in STP primary effluents with median concentrations in the range of 5-20 ng/L, but peak concentrations up to 1 μg/L. N-nitrosomorpholine (NMOR) was abundant in all plants at concentrations of 5-30 ng/L, other nitrosamines occurred at a lower number of plants at similar levels. From concentrations in urine samples and domestic wastewater we estimated that human excretion accounted for levels of <5 ng/L of NDMA and <1 ng/L of the other nitrosamines in municipal wastewater, additional domestic sources for <5 ng/L of NMOR. Levels above this domestic background are probably caused by industrial or commercial discharges, which results in highly variable concentrations in sewage. Aqueous removal efficiencies in activated sludge treatment were in general above 40% for NMOR and above 60% for the other nitrosamines, but could be lower if concentrations were below 8-15 ng/L in primary effluent. We hypothesize that substrate competition in the cometabolic degradation explains the occurrence of such threshold concentrations. An additional sand filtration step resulted in a further removal of nitrosamines from secondary effluents even at low concentrations. Concentrations released to surface waters were largely below 10 ng/L, suggesting a low impact on Swiss water resources and drinking water generation considering the generally high environmental dilution and possible degradation. However, local impacts in case a larger fraction of wastewater is present cannot be ruled out.     

Sulfamethoxazole contamination of a deep phreatic aquifer

Groundwater samples were obtained from the water table region of a phreatic aquifer (unsaturated zone depth up to 28 m) under land irrigated with wastewater effluents for about 5 decades and a relatively deep pumping well (109 m), used as a drinking water source till 2007, located downstream (1300 m) of wastewater effluent and sludge infiltration facilities. Sulfamethoxazole (SMX) concentrations in secondary effluents varied between 90 and 150 ng/L. SMX was extracted using SPE and was analyzed by HPLC-MS/MS. SMX (maximum concentration of 37 ng/L) was detected in the water table region, in two monitoring wells, after an unsaturated zone transport period of about 16 years. The maximum SMX concentration detected in the pumping well was of 20 ng/L. These results question wastewater effluent disposal strategies including the suitability of irrigation with effluents on the replenishment area of an aquifer supplying drinking water.     

Mercury speciation in the Valdeazogues River-La Serena Reservoir system: Influence of Almadén (Spain) historic mining activities

Mercury (Hg) speciation and partitioning have been investigated in a river-reservoir system impacted by the Almadén mining activities, the world's largest Hg district. This study is the first to simultaneously investigate Hg dynamics from above the mining district and into the La Serena Reservoir (3219 Hm³), being the third largest reservoir in Europe and the largest in Spain.Water, sediment and biota were sampled at different seasons during a 2-year study from the Valdeazogues River, which flows east-west from the mining District, to La Serena Reservoir. Simultaneously, a comprehensive study was undertaken to determine the influence of some major physico-chemical parameters that potentially influence the fate of Hg within the watershed.Concentrations of dissolved Hg in water were below 0.14 µg/L, whereas particulate Hg ranged from 0.1 to 87 µg/g, with significant seasonal variation. Total Hg concentrations varied from 7 to 74 µg/g in sediment from the Valdeazogues River, while in sediments from La Serena Reservoir were below 2 µg/g. On the other hand, methyl-Hg reached concentrations up to 0.3 ng/L in water and 6 ng/g in sediment from La Serena Reservoir, whereas maximum concentrations in Valdeazogues River were 5 ng/L and 880 ng/g in water and sediment, respectively. The distribution of Hg species in the Valdeazogues River-La Serena Reservoir system indicated a source of Hg from the mine waste distributed along the river. Total Hg in water was strongly correlated with total dissolved solids and chlorophyll a concentrations, whereas organic carbon and Fe concentrations seem to play a role in methylation of inorganic Hg in sediment. Total Hg concentrations were low in fish from Valdeazogues River (0.8-8.6 ng/g, wet weight) and bivalves from La Serena Reservoir (10-110 ng/g, wet weight), but most was present as methyl-Hg.     

Factors affecting methylmercury distribution in surficial, acidic, base-metal mine tailings

The most toxic form of Hg commonly of concern in the environment is methylmercury (MeHg), as it accumulates in living tissues and bioconcentrates in food webs. Sulfide-rich metal ores are often enriched in Hg, but little is known regarding the potential for Hg methylation in acidic tailings produced from these ores. This study examined acidic tailings from four mines in northern Ontario, Canada, to determine whether they could be an important source of MeHg to downstream environments. Where sulfate reducing bacteria (SRB) were abundant and active in pH-circumneutral, unoxidized layers (Potter mine), negligible MeHg was detected. By contrast, a zone of active sulfate reduction found in the acidic, oxidizing, surficial layers of tailings from the Kidd Metsite contained the highest concentrations of MeHg in bulk tailings (12.1 nmol kg(-1) dry wt. of sediment) and porewaters (88 pM) measured in this study. Cell count estimates of SRB by the "most-probable-number" (MPN) method were low in these surficial tailings, suggesting that sulfate reducers from this environment were acidophilic and did not thrive under the pH-neutral conditions of the MPN incubations. A later study of bacterial DNA from these tailings produced evidence of a novel Deltaproteobacterium which has only previously been detected in acid mine drainage environments. Further research will be necessary to determine whether this Deltaproteobacterium is a sulfate reducer and/or an efficient Hg methylator. Surface water concentrations of MeHg did not exceed Canadian water quality guidelines at any of the sites sampled, but one site (Broulan) featured total Hg (HgT) concentrations of 838 pM in filtered samples, far in excess of recommended levels. Trends in surface water MeHg and HgT reflected corresponding values in porewaters from the same sites, indicating that concentrations of these substances in tailings influence surface water concentrations.     

An analytical protocol for the determination of total mercury concentrations in solid peat samples

Traditional peat sample preparation methods such as drying at high temperatures and milling may be unsuitable for Hg concentration determination in peats due to the possible presence of volatile Hg species, which could be lost during drying. Here, the effects of sample preparation and natural variation on measured Hg concentrations are investigated. Slight increases in mercury concentrations were observed in samples dried at room temperature and at 30 degrees C (6.7 and 2.48 ng kg(-1) h(-1), respectively), and slight decreases were observed in samples dried at 60, 90 and 105 degrees C (2.36, 3.12 and 8.52 ng kg(-1) h(-1), respectively). Fertilising the peat slightly increased Hg loss (3.08 ng kg(-1) h(-1) in NPK-fertilised peat compared to 0.28 ng kg(-1) h(-1) in unfertilised peat, when averaged over all temperatures used). Homogenising samples by grinding in a machine also caused a loss of Hg. A comparison of two Hg profiles from an Arctic peat core, measured in frozen samples and in air-dried samples, revealed that no Hg losses occurred upon air-drying. A comparison of Hg concentrations in several plant species that make up peat, showed that some species (Pinus mugo, Sphagnum recurvum and Pseudevernia furfuracea) are particularly efficient Hg retainers. The disproportionally high Hg concentrations in these species can cause considerable variation in Hg concentrations within a peat slice. The variation of water content (1.6% throughout 17-cm core, 0.97% in a 10 x 10 cm slice), bulk density (40% throughout 17-cm core, 15.6% in a 10 x 10 cm slice) and Hg concentration (20% in a 10 x 10 cm slice) in ombrotrophic peat were quantified in order to determine their relative importance as sources of analytical error. Experiments were carried out to determine a suitable peat analysis program using the Leco AMA 254, capable of determining mercury concentrations in solid samples. Finally, an analytical protocol for the determination of Hg concentrations in solid peat samples is proposed. This method allows correction for variation in factors such as vegetation type, bulk density, water content and Hg concentration in individual peat slices. Several subsamples from each peat slice are air dried, combined and measured for Hg using the AMA254, using a program of 30 s (drying), 125 s (decomposition) and 45 s (waiting). Bulk density and water content measurements are performed on every slice using separate subsamples.