Assessing potential bioavailability of metals in sediments: A proposed approach

Due to anthropogenic inputs, elevated concentrations of metals frequently occur in aquatic sediments. In order to make defensible estimates of the potential risk of metals in sediments and/or develop sediment quality criteria for metals, it is essential to identify that fraction of the total metal in the sediments that is bioavailable. Studies with a variety of benthic invertebrates indicate that interstitial (pore) water concentrations of metals correspond very well with the bioavailability of metals in test sediments. Many factors may influence pore water concentrations of metals; however, in anaerobic sediments a key phase controlling partitioning of several cationic metals (cadmium, nickel, lead, zinc, copper) into pore water is acid volatile sulfide (AVS). In this paper, we present an overview of the technical basis for predicting bioavailability of cationic metals to benthic organisms based on pore water metal concentrations and metal-AVS relationships. Included are discussions of the advantages and limitations of metal bioavailability predictions based on these parameters, relative both to site-specific assessments and the development of sediment quality criteria.     

SUSPENDED SEDIMENT AND METALS REMOVAL FROM URBAN RUNOFF BY A SMALL LAKE1

ABSTRACT: A small lake in the Chicago Metropolitan Area was from 91 to 95 percent efficient in removing suspended sediment and from 76 to 94 percent efficient in removing copper, iron, lead, and zinc from urban runoff. Sediments accumulated in the lake in the form of an organic-rich mud at an average rate of 20 millimeters per year; this reduced lake storage and covered potential habitat for aquatic organisms. Copper, lead, and zinc concentrations were closely associated with suspended-sediment concentrations and with silt- and clay-sized fractions of lake sediment. Although concentrations of mercury and cadmium were near detection limits in runoff, measurable concentrations of these metals accumulated in the lake sediments.     

GOLD-MINING EFFECTS ON HEAVY METALS IN STREAMS,CIRCLE QUADRANGLE,ALASKA1

Placer gold mining, which extracts gold from buried or exposed alluvia, is often conducted on or near streams. Such mining has the potential to adversely affect water quality. Other heavy metals associated with the gold (such as arsenic, cadmium, lead, zinc, and copper) may be freed to enter streams. Mercury may also enter streams if miners are using it to recover fine particles of gold. These heavy metals are toxic and thus may be harmful to the aquatic life of the streams receiving effluent or runoff from placer mines. In 1982 we sampled two streams intensively - one heavily mined and one unmined - for total recoverable arsenic, mercury, lead, zinc, and copper. Only mercury was not significantly higher in concentration in the mined streams. In 1983 we sampled two stream pairs three times, and 10 other sites at least once, for total and dissolved arsenic, cadmium, mercury, lead, zinc, and copper. Mercury and cadmium were not significantly elevated in mined streams, but the concentrations of total arsenic, lead, zinc, and copper, and dissolved arsenic and zinc were significantly higher in streams below active placer mining sites than in these that were not being mined or those that had never been mined. Additionally, total arsenic, lead, zinc, and copper and dissolved arsenic and copper became elevated after mining began in 1983 on a previously unmined stream.     

Landscape metrics and estuarine sediment contamination in the mid-Atlantic and southern New England regions

In a previously published study, quantitative relationships were developed between landscape metrics and sediment contamination for 25 small estuarine systems within Chesapeake Bay. These analyses have been extended to include 75 small estuarine systems across the mid-Atlantic and southern New England regions of the USA. Because of the different characteristics and dynamics of the estuaries across these regions, adjustment for differing hydrology, sediment characteristics, and sediment origins were included in the analysis. Multiple linear regression with stepwise selection was used to develop statistical models for sediment metals, organics, and total polycyclic aromatic hydrocarbons (PAHs). The landscape metrics important for explaining the variation in sediment metals levels (R2 = 0.72) were the percent area of nonforested wetlands (negative contribution), percent area of urban land, and point source effluent volume and metals input (positive contributions). The metrics important for sediment organics levels (R2 = 0.5) and total PAHs (R2 = 0.46) were percent area of urban land (positive contribution) and percent area of nonforested wetlands (negative contribution). These models included silt-clay content (metals) or total organic C (organics, total PAHs) of sediments and grouping by estuarine hydrology, suggesting the importance of sediment characteristics and hydrology in mitigating the influence of the landscape metrics on sediment contamination levels. The overall results from this study are indicative of how statistical models can be developed relating landscape metrics to estuarine sediment contamination for distributions of land cover and point source discharges.     

INPUTS OF COPPER‐BASED CROP PROTECTANTS TO COASTAL CREEKS FROM PASTICULTURE RUNOFF1

ABSTRACT: Inputs of copper‐based crop protectants from tomato fields grown under plastic mulch agriculture (plasticulture) to an estuarine creek were investigated. Copper was measured in runoff from diverse land‐uses including conventional agriculture, plasticulture, residences, and natural areas. Water column and sediment copper concentrations were measured in plasticulture and control (nonagriculture) watersheds. Copper concentrations in plasticulture‐impacted creeks exceeded background levels episodically. High concentrations occurred during or immediately after runoff‐producing rains. Concentrations of 263 μg/L total copper and 126 μg/L dissolved copper were measured in a tidal creek affected by plasticulture; concentrations exceeded the shellfish LC₅₀ values and the water quality criteria of 2.9 μg/L dissolved copper. Control watersheds indicated background water column levels of ≤ 4 μg/L dissolved copper with similar copper levels during periods with and without rain. The copper concentrations in tomato plasticulture field runoff itself contained up to 238 μg/L dissolved copper. Copper concentrations in runoff from other land‐uses were less than 5 μg/L dissolved copper. Creek sediment samples adjacent to a plasticulture field contained significantly higher copper concentrations than sediments taken from nonplasticulture watersheds.     

EVALUATION OF PHILODINA ACUTICORNIS (ROTIFERA) AS A BIOASSAY ORGANISM FOR HEAVY METALS1

ABSTRACT: A technique for using the rotifer Philodina acuticornis as a bioassay organism is described. The rotifer was exposed to a range of concentrations for each of 14 toxicants. The effects of the heavy metals cadmium, chromium, cobalt, copper, lead, mercury, nickel, silver and zinc were studied. Based upon 96 hours exposure in soft water the sensitivity of the rotifer to the metals from the most toxic to least toxic was: cadmium, mercury and copper, zinc, silver, nickel (chloride), chromium, nickel (sulfate), lead and colbalt. In hard water with 96 hours exposure the most to least toxic respectively were: cadmium, copper, mercury, chromium and lead. The 48 hour EC₅₀ value suggests that zinc will follow mercury in relative toxicity when Philodina is tested in hard water. In a comparison of the toxicity of the chloride and sulfate salts of cadmium, nickel and zinc in soft water cadmium sulfate and zinc sulfate were more toxic after 96 hours; nickelous chloride was more toxic than nickelous sulfate. Increased water hardness decreased the toxicity of the heavy metals studied. The results suggest that this rotifer may be more sensitive than the bluegill sunfish to the salts of cadmium, copper, nickel, zinc and chromium and less sensitive to lead. Data for cobalt, silver and mercury were not available. Philodina was extremely tolerant of ammonium chloride and phenol. The feasibility and economics of using an inexpensive, readily cultured and available organism such as Philodina acuticornis as a bioassay organism were discussed.     

DISSOLVED HEAVY METALS IN SHALLOW GROUND WATER IN A SOUTHEASTERN MICHIGAN URBAN WATERSHED1

ABSTRACT: The occurrence of dissolved heavy metal concentrations in shallow ground water were measured at 126 sites within an urban watershed in southeastern Michigan. A total of 1,140 samples were collected from the first saturated zone, and the mean concentrations of 11 heavy metals (arsenic, barium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, and zinc) were obtained and compared to their corresponding mean concentrations within surface soil. The results suggest that former and current land use processes have resulted in significant adverse impacts on the study region. Levels of Cr 20 to 30 times the maximum contaminant level (MCL) have been detected in the ground water beneath industrial sites. In addition, Cd and Pb have been found at levels exceeding their MCLs where surface soils are clay‐rich, and in sandy soils at more than 10 times their MCLs. The high levels of Cr in ground water strongly suggest that the chromium is in a hexavalent form, and this likelihood is supported by current studies. Given the hydraulic connection between the watershed's surface waters and the Great Lakes, these findings raise significant ecological and public health concerns.     

FACTORS INFLUENCING ACUTE TOXICfrY OF COAL ASH TO RAINBOW TROUT (SALMO GAIRDNERI) AND BLUEGILL SUNFISH (LEPOMIS MACROCHIRUS)1

ABSTRACT: The potentially toxic components in coal ash (ash particles, heavy metals) were evaluated in laboratory static, acute (96 hr) bioassays, both separately and in various combinations with extreme pH (5.0 and 8.5), using rainbow trout (Salmo gairdneri) and bluegifi sunfish (Lepomis macrochirus). Ash particle morphology and metal distribution anlaysis, using electron microscopy and surface-subsurface analysis by ion microscopy, showed that metals could be either clumped or evenly distributed on the surface of fly ash. Surface enrichment on fly ash particles from electrostatic precipitators, as measured by ion microscopy, was found for cadmium, copper, chromium, nickel, lead, mercury, titanium, arsenic, and selenium. Bottom (heavy) ash was not acutely toxic to either fish species at concentrations of up to 1500 mg/l total suspended solids (TSS) at pH 5.0, 7.5, or 8.5. Fly ash particles were not acutely toxic to blue-gill at levels up to 1360 mg/l TSS. Rainbow trout were highly sensitive to fly ash (25 to 60 percent mortality) at concentrations of 4.3 to 20.5 mg/I TSS when dissolved metal availability was high but were not sensitive at higher particulate concentrations (58 to 638 mg/I TSS) when dissolved metals were low. When metals were acid-leached from fly ash prior to testing, no rainbow trout mortality occurred at TSS concentrations of up to 2,350 mg/l TSS. When the percent of dissolved metal was high (e.g., 50–90 percent of the total), fish mortality was increased. Rainbow trout were nearly two orders of magnitude more sensitive than bluegill when subjected to a blend of cadmium, chromium, copper, nickel, lead, and zinc. The two species were similar in their acute sensitivity to acidic pH at levels at or below 4.0 and alkaline pH of 9.1. If the pH of coal ash effluent is contained within the range 6.0 to 9.0, acute toxicity to fish can be attributed to trace element availability from fly ash but not heavy ash. Control of holding pond and effluent pH and maximizing pond residence time are important strategies for minimizing effects of ash pond discharges on fish.     

Metals distribution and interactions in tissues of shrews (Sorex spp.) from copper- and zinc-contaminated areas in Poland

To assess the risk from heavy metal accumulation to insectivorous species exposed to different pollutants, shrews [Sorex araneus (Linnaeus 1758) and Sorex minutus (Linnaeus 1766)] were collected in the Olkuski Ore Region (OOR; a Zn and Cd smelter area), Legnicko-G?ogowski Copper Mine Region (LGCR; a copper ore-mining area), and Bia?owieza Forest (BF; a control area). A few sites were chosen in each region and a total of 57 animals were collected from them. The liver and kidneys were dissected from the animals, dried, and digested in a 4:1 mixture of HNO3 (nitric acid) and HClO4 (perchloric acid). Cadmium, lead, zinc, copper, and iron were determined in the samples by flame or flameless atomic absorption spectrometry. The interactions between toxic and essential metals were calculated for each tissue. The data showed that accumulation of metals by insectivores is high; shrews accumulated much higher amounts of cadmium and lead than bank voles, studied by other researchers, from the same areas. The expected high tissue accumulation of copper at LGCR and zinc at OOR was not seen, but the levels of both elements were higher in the tissues of shrews from OOR than from LGCR. The lowest copper concentrations were in the tissues of shrews from BF. The highest cadmium and lead concentrations were found in the tissues of shrews from OOR. Some significant correlations were found between the tissue concentrations of xenobiotic and essential metals (e.g., between cadmium and zinc and between lead and iron).     

Heavy metals in an urban watershed in southeastern Michigan

The occurrence of heavy metals in the soil was measured over a period of several years to determine background concentrations in a heavily urbanized watershed in southeastern Michigan. A spatially dispersed sample was collected to capture the inherent variability of the soils and historic land use. The analysis focused on 14 metals (antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, thallium, and zinc) that are part of the USEPA's list of the 129 most common pollutants. Metal concentrations were measured at three depths: near-surface (<0.5 m), shallow subsurface (0.5-10 m), and depths greater than 10 m across six soil units in glacial terrain. Additional analyses assessed the metal concentrations in each depth profile across three general land use categories: residential, commercial, and industrial. Metal concentrations were the highest in the near-surface with Pb present at concentrations averaging 15.5 times that of background in industrial areas and approximately 16 times background in residential areas. Cadmium, Hg, and Zn were also present in surface soils at levels of several times that of background. The highest concentrations of each of these metals were present in the clay-rich soils located in the eastern, more urbanized and industrialized part of the watershed. Metals detected at elevated concentrations decreased in concentration with increasing depth and distance from the urbanized and industrialized center of the watershed. Statistically significant differences in the concentrations of heavy metals were also noted between the land use categories, with Cd, Cr, Cu, Pb, Ni, and Zn observed within industrial areas at mean concentrations several times greater than background levels.     

Geochemical partitioning of copper, lead, and zinc in benthic, estuarine sediment profiles

The geochemical partitioning of copper (Cu), lead (Pb), and zinc (Zn) was examined in benthic sediment profiles (0- to 20-cm depth interval) composed of relatively coarse (65-90% sand-sized particles), noncohesive, suboxic material (Eh +120 to +260 mV). Total Cu, Pb, and Zn concentrations ranged from 8.3 to 194, 16.3 to 74.8, and 30.1 to 220 mg/kg, respectively, and were related to vertical trends in sediment texture. The observed distribution coefficients describing solid-solution partitioning were in the range of 100 to 1000 L/kg. The geochemical partitioning of solid-phase Cu, Pb, and Zn between six operationally defined fractions was examined with a sequential extraction scheme. The association of Cu, Pb, and Zn with amorphous oxides, crystalline oxides, and organic matter was linearly dependent on the abundance of each respective phase. For retention by amorphous oxide minerals, the observed stoichiometry ranged from 5.2 to 23.7 mg/g for Cu, 12.8 to 21.5 mg/g for Pb, and 23.1 to 85.7 mg/g for Zn. Corresponding values for association with crystalline oxides were an order of magnitude less than those for amorphous oxides, indicating a lesser affinity of trace metals for crystalline oxides. The stoichiometric relationships describing association with organic matter ranged from 17.6 to 54.0 mg/g for Cu, 6.1 to 9.6 mg/g for Pb, and 6.4 to 16.4 mg/g for Zn. The results from this study provide an insight into processes controlling trace metal partitioning in coarse-textured, suboxic, estuarine sediments.     

Models of total and presumed wildlife sources of fecal coliform bacteria in coastal ponds

Models that accurately predict fecal coliform bacteria (FCB) concentrations, one of the most widely used measures of estuarine water quality, are needed to improve land use decision-making. Rapidly occurring changes in coastal land uses and the influence on water quality increases the urgency of having improved decision tools. For this study, samples were collected monthly from six coastal ponds, two tidal creeks and four shallow water wells for up to 212 years. These data were used along with other measures of environmental conditions and land classes within each watershed to construct quantitative relationships between combinations of variables and both total and presumed wildlife sources of FCB. Linear regression, bootstrapping and generalized additive modeling that incorporates both linear and nonlinear terms were used. Results of repeated simultaneous sampling on the same tide stage of ponds and downstream estuarine creeks suggest that most FCB come from wildlife and that the ponds effectively remove these bacteria except immediately following heavy rainfall. Predictive models for concentrations of total and presumed wildlife bacteria are provided along with simple measures to estimate watershed boundaries. It is proposed that these tools can be used to minimize impacts on receiving water body quality. The models can be used to test alternative development approaches within coastal watersheds similar to that found in the southeastern USA coastal zone as well as to evaluate specific proposed landscape alterations.     

规模化农田土壤重金属污染修复的中试试验研究——以某镇土壤污染治理为例

农用地重金属污染长期以来一直是生态环境的热点和难点问题。2017年,对某镇农田土壤重金属污染开展详查,单项污染指数评价结果表明,镉超标率为67.60%(Pi>1),基于内梅罗污染指数法的评价结果显示,57.30%的点位受到不同程度的污染(PN≥1.0);2018年,分别选取钝化修复和植物修复进行中试试验,经钝化修复后土壤有效镉和总镉含量分别平均降低32.73%和5.64%。经超富集植物籽粒笕种植一季修复后,土壤总镉含量降低15%以上。本次中试试验修复效果良好,能为下一阶段的土壤镉污染修复方案的制定和优化提供科学的依据,为全国农用地重金属污染修复提供了有价值的借鉴意义。     

规模化农田土壤重金属污染修复的中试试验研究——以某镇土壤污染治理为例

农用地重金属污染长期以来一直是生态环境的热点和难点问题。2017年,对某镇农田土壤重金属污染开展详查,单项污染指数评价结果表明,镉超标率为67.60%(Pi>1),基于内梅罗污染指数法的评价结果显示,57.30%的点位受到不同程度的污染(PN≥1.0);2018年,分别选取钝化修复和植物修复进行中试试验,经钝化修复后土壤有效镉和总镉含量分别平均降低32.73%和5.64%。经超富集植物籽粒笕种植一季修复后,土壤总镉含量降低15%以上。本次中试试验修复效果良好,能为下一阶段的土壤镉污染修复方案的制定和优化提供科学的依据,为全国农用地重金属污染修复提供了有价值的借鉴意义。     

Incidence of adverse biological effects within ranges of chemical concentrations in marine and estuarine sediments

Matching biological and chemical data were compiled from numerous modeling, laboratory, and field studies performed in marine and estuarine sediments. Using these data, two guideline values (an effects range-low and an effects range-median) were determined for nine trace metals, total PCBs, two pesticides, 13 polynuclear aromatic hydrocarbons (PAHs), and three classes of PAHs. The two values defined concentration ranges that were: (1) rarely, (2) occasionally, or (3) frequently associated with adverse effects. The values generally agreed within a factor of 3 or less with those developed with the same methods applied to other data and to those developed with other effects-based methods. The incidence of adverse effects was quantified within each of the three concentration ranges as the number of cases in which effects were observed divided by the total number of observations. The incidence of effects increased markedly with increasing concentrations of all of the individual PAHs, the three classes of PAHs, and most of the trace metals. Relatively poor relationships were observed between the incidence of effects and the concentrations of mercury, nickel, total PCB, total DDT and p,p′-DDE. Based upon this evaluation, the approach provided reliable guidelines for use in sediment quality assessments. This method is being used as a basis for developing National sediment quality guidelines for Canada and informal, sediment quality guidelines for Florida. The methods and guidelines presented in this report do not necessarily represent the policy of the National Oceanic and Atmospheric Administration, Environment Canada, or Florida Department of Environmental Protection.     

ACCUMULATION OF SELECTED TRACE METALS IN SOILS OF URBAN RUNOFF SWALE DRAINS1

ABSTRACT: Field investigations were conducted at three sites in the Washington, D.C., area to detect the accumulation patterns of the trace metals, cadmium, copper, lead and zinc in the soils of roadside grassed swale drains that had been receiving urban stormwater runoff. Two sites were residential areas and one site was an intensively used highway. The research results seem to indicate that the use of swale drains to control urban stormwater runoff had few harmful effects to fine textured soils with respect to the study metals. With the exception of zinc, typical roadside patterns of decreasing metal concentrations with increasing distance from roads were observed for the upper 5 cm of study soils. Zinc accumulated in residential grassed swales due to leachate from galvanized curverts. Sampling to a depth of 60 cm revealed no evidence of subsurface trace metal enrichment in the study swales. Although the percentage of soil zinc in leachable form was as high as 20 percent of total zinc concentrations, the other study metals had small leachable components. Leachable lead was always less than 1 percent of the total lead.     

Trace metal contents of the pacific oyster (Crassostrea gigas) purchased from markets in Hong Kong

Arsenic, cadmium, chromium, and copper concentrations of the Pacific oyster,Crassostrea gigas, purchased from four different markets were determined in this project. In general, gill tissue had the highest proportion of metal contents (34%–67%) when compared with other tissue parts (mantle, viscera, and adductor muscle), except for arsenic, which showed the highest level in adductor muscle (44%). Smaller oysters (longitudinal length of soft body part less than 6 cm) had higher metal levels than larger ones (longitudinal length of soft body part more than 6 cm), except copper. None of the four metals examined showed an obvious seasonal trend, although cadmium levels seemed to be higher in autumn and winter months. Arsenic, cadmium, and copper levels in oysters purchased from different markets and different months obtained in the present study were higher when compared with past reports. Cadmium levels, as high as 10.98 mg/kg (dry weight basis) have been obtained. This approaches the safety limit that may be hazardous to human health. Continual monitoring of cadmium and other trace metals of toxicological significance to man in Hong Kong seafood is recommended.     

土壤重金属污染及其修复技术研究

土壤重金属污染物有汞、镉、铅、锌等,主要来源于交通运输、工业污染和农业污染。土壤重金属污染会导致农作物减产甚至死亡,对人体健康也会产生极大危害。目前土壤重金属污染修复的技术主要包括工程修复法、物理化学修复法、化学修复法和生物修复法。植物修复技术作为一种新兴的绿色、生态、高效的修复技术具有良好的发展前景。     

Influence of nutrient levels on uptake and effects of mercury, cadmium, and lead in water spinach

In Southeast Asia the aquatic macrophyte water spinach (Ipomoea aquatica Forsk.) is a popular vegetable that is cultivated in freshwater courses. These often serve as recipients for domestic and other sorts of wastewater that often contain a variety of pollutants, such as heavy metals. In addition, fertilizers are frequently used where water spinach is cultivated commercially for the food market. To estimate the importance of ambient nutrient concentrations for accumulation of mercury (Hg), cadmium (Cd), and lead (Pb) in water spinach, plants were exposed to nutrient solutions of different strength and with varying metal concentrations. Metal-induced toxic effects, which might possibly affect the yield of the plants, were also studied. The lower the nutrient strength in the medium was, the higher the metal concentrations that accumulated in the different plant parts and the lower the metal concentration in the medium at which metal-induced toxic effects occurred. Accordingly, internal metal concentrations in the plants were correlated to toxic effects. Plants exposed to metals retained a major proportion of the metals in the roots, which had a higher tolerance than shoots for high internal metal concentrations.     

pH-dependent release of cadmium,copper, and lead from natural and sludge-amended soils

The pH-dependent release of cadmium, copper, and lead from soil materials was studied by use of a stirred flow cell to quantify their release and release rates, and to evaluate the method as a test for the bonding strength and potential mobility of heavy metals in soils. Soil materials from sludge-amended and nonamended A horizons from a Thai coarse-textured Kandiustult and a Danish loamy Hapludalf were characterized and tested. For each soil sample, release experiments with steady state pH values in the range 2.9 to 7.1 and duration of 7 d were performed. The effluent was continuously collected and analyzed. Release rates and total releases were higher for the Hapludalf than the Kandiustult and higher for the sludge-amended soils than the nonamended soils. With two exceptions the relative release rates (release rate/total content of metal in soil) plotted vs. steady state pH followed the same curves for each metal, indicating similar bonding strengths. These curves could be described by a rate expression of the form: relative release rate = k[H+]a, with specific a (empirical constant) and k (rate constant) parameters for each metal demonstrating that metal release in these systems can be explained by proton-induced desorption and dissolution reactions. With decreasing pH, pronounced increases in release rates were observed in the sequence cadmium > lead > copper, which express the order of metal lability in the soils. The flow cell system is useful for comparison of metal releases as a function of soil properties, and can be used as a test to rank soils with respect to heavy metal leaching.