Assessment of arsenic and heavy metal concentrations in water and sediments of the Rio Grande at El Paso-Juarez metroplex region

The Rio Grande located along the US-Mexico border is affected by anthropogenic activities along its geographical course. Runoff and wind deposition of smelting residues may contribute to the pollution of the Rio Grande in the El Paso-Ciudad Juarez area. Few studies have addressed the presence or impacts of heavy metals or arsenic in this ecosystem. This study reports a survey of heavy metals (Cr, Cu, Cd, Ni, Pb, and Zn) and arsenic (As) in water and sediments of the Rio Grande collected from seven sites in the El Paso-Juarez region. Since water quality influences metal content in water, physical (temperature, flow and conductivity), and chemical (pH, dissolved oxygen, nitrates, alkalinity, and water hardness) parameters were measured at each site. Arsenic and heavy metal levels were determined using Inductively Couple Plasma (ICP) emission spectroscopy following EPA procedures. Zinc and lead were found as both total and dissolved metals in most of the samples, with concentrations of total recoverable metals reaching up to 105 and 70 microg/l, respectively. Most metals were found in sediment samples collected from four of seven sites. The highest Cu concentration (35 mg/l) was found at the American Dam site. Concentrations of metals found through this survey will be used as a reference for future studies in monitoring arsenic, heavy metals, and their impacts in the Rio Grande.     

Using FTIR to corroborate the identity of functional groups involved in the binding of Cd and Cr to saltbush (Atriplex canescens) biomass

Fourier transform infrared (FTIR) studies were performed to confirm the chemical modification of saltbush (Atriplex canescens) biomass and to provide information about the identity and binding characteristics of the chemical groups responsible for the binding of Cd(II), Cr(III), and Cr(VI). In addition, studies were performed to determine the optimum time for the binding of the three ions by saltbush biomass, and to study the efficiency of HCl and sodium citrate as stripping agents. The metal quantification was performed using inductively coupled plasma optical emission spectroscopy (ICP-OES). The results showed that 10 min or less is enough to achieve the maximum metal binding, and that aqueous solutions of 0.1 mM HCl or sodium citrate were enough to strip more than 80% of the bound Cd. It was determined that more than 70% of the bound Cr(III) was stripped using 0.1 mM HCl. Chemical modification of carboxyl and ester groups on the biomass was performed. The FTIR results confirmed that the esterification of carboxyl groups and hydrolysis of ester groups in the native biomass had occurred. The direct effect of these modifications on the binding properties of the biomass provided strong evidence that the carboxyl functionality is the main group responsible for binding Cd and Cr(III). However, the IR data showed that for Cr(VI), a different type of functional group is involved.     

Accumulation, speciation and cellular localization of copper in Sesbania drummondii

Growth, accumulation and intracellular speciation and distribution of copper (Cu) in Sesbania drummondii was studied using scanning-electron microscopy (SEM), X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). The growth of seedlings was assessed in terms of biomass accumulation. The growth of the seedling was enhanced by 73.5% at a low Cu concentration (50 mg l⁻¹) compared to the control treatment. Additionally, seedling growth was inhibited by 18% at 300 mg l⁻¹ Cu with respect to the control. Copper concentration in roots and shoots was increased with increasing Cu concentration in the growth solution. The accumulation of Cu was found to be higher in roots than in the shoots. At a concentration of 300 mg l⁻¹ Cu, the roots accumulated 27,440 mg Cu kg⁻¹ dry weight (dw) while shoots accumulated 1282 mg Cu kg⁻¹ dw. Seedlings were assessed for photosynthetic activity by measuring chlorophyll a fluorescence parameters: F_v/F_m and F_v/F₀ values. Photosynthetic integrity was not affected by any of the Cu treatments. The X-ray absorption spectroscopic (XAS) studies showed that Cu was predominantly present as Cu(II) in Sesbania tissue. In addition, from the XAS studies it was shown that the Cu exists in a mixture of different coordination states consisting of Cu bound to sugars and small organic acids with some possible precipitated copper oxide. From the EXAFS studies, the coordination of Cu was determined to have four equatorial oxygen(nitrogen) ligands at 1.96 Å and two axial oxygen ligands at 2.31 Å. Scanning-electron microscopy studies revealed the distribution of Cu within the seedlings tissues, predominantly accumulated in the cortical and vascular (xylem) regions of root tissues. In the stem, most of the Cu was found within the xylem tissue. However, the deposition of Cu within the leaf tissues was in the parenchyma. The present study demonstrates the mechanisms employed by S. drummondii for Cu uptake and its biotransformation.     

Cadmium uptake and translocation in tumbleweed (Salsola kali), a potential Cd-hyperaccumulator desert plant species: ICP/OES and XAS studies

Cadmium is a heavy metal, which, even at low concentrations, can be highly toxic to the growth and development of both plants and animals. Plant species vary extensively in their tolerance to excess cadmium in a growth medium and very few cadmium-tolerant species have been identified. In this study, tumbleweed plants (Salsola kali) grown in an agar-based medium with 20 mgl(-1) of Cd(II) did not show phytotoxicity, and their roots had the most biomass (4.5 mg) (P < 0.05) compared to the control plants (2.7 mg) as well as other treated plants. These plants accumulated 2696, 2075, and 2016 mg Cd kg(-1) of dry roots, stems, and leaves, respectively. The results suggest that there is no restricted cadmium movement in tumbleweed plants. In addition, the amount of Cd found in the dry leaf tissue suggests that tumbleweed could be considered as potential cadmium hyperaccumulating species. X-ray absorption spectroscopy studies demonstrated that in roots, cadmium was bound to oxygen while in stems and leaves, the metal was attached to oxygen and sulfur groups. This might imply that some small organic acids are responsible for Cd transport from roots to stems and leaves. In addition, it might be possible that the plant synthesizes phytochelatins in the stems, later coordinating the absorbed cadmium for transport and storage in cell structures. Thus, it is possible that in the leaves, Cd either exists as a Cd-phytochelatin complex or bound to cell wall structures. Current studies are being performed in order to elucidate the proposed hypothesis.     

Screening the phytoremediation potential of desert broom (Baccharis sarothroides Gray) growing on mine tailings in Arizona, USA

The metal concentrations in a copper mine tailings and desert broom (Baccharis sarothroides Gray) plants were investigated. The metal concentrations in plants, soil cover, and tailings were determined using ICP-OES. The concentration of copper, lead, molybdenum, chromium, zinc, arsenic, nickel, and cobalt in tailings was 526.4, 207.4, 89.1, 84.5, 51.7, 49.6, 39.7, and 35.6mgkg(-1), respectively. The concentration of all elements in soil cover was 10-15% higher than that of the tailings, except for molybdenum. The concentration of copper, lead, molybdenum, chromium, zinc, arsenic, nickel, and cobalt in roots was 818.3, 151.9, 73.9, 57.1, 40.1, 44.6, 96.8, and 26.7mgkg(-1) and 1214.1, 107.3, 105.8, 105.5, 55.2, 36.9, 30.9, and 10.9mgkg(-1) for shoots, respectively. Considering the translocation factor, enrichment coefficient, and the accumulation factor, desert broom could be a potential hyperaccumulator of Cu, Pb, Cr, Zn, As, and Ni.     

Analysis of Temporal and Spatial Dichotomous PM Air Samples in the El Paso-Cd. Juarez Air Quality Basin

ABSTRACT

This paper presents and discusses the results obtained from the gravimetric and chemical analyses of the 24-hr average dichotomous samples collected from five sites in the El Paso-Cd. Juarez air quality basin between August 1999 and March 2000. Gravimetric analysis was performed to determine the temporal and spatial variations of PM_2.5 (particulate matter less than 2.5 um in diameter) and PM2.5-10 (particulate matter less than 10 μm but greater than 2.5 μm in diameter) mass concentrations. The results indicate that ~25% of the PM10 (i.e., PM2.5 + PM2.5-10) concentration is composed of PM2.5. Concurrent measurements of hourly PM concentrations and wind speed showed strong diurnal patterns of the regional PM pollution. Results of X-ray fluorescence (XRF) elemental analyses were compared to similar but limited studies performed by the Texas Natural Resource Conservation Commission (TNRCC) in 1990 and 1997. Major elements from geologic sources—Al, Si, Ca, Na, K, Fe, and Ti—accounted for 35% of the total mass concentrations in the PM2.5-10 fraction, indicating that geologic sources in the area are the dominant PM sources. Levels of toxic trace elements, mainly considered as products of anthropogenic activities, have decreased significantly from those observed in 1990 and 1997.     

Speciation and uptake of arsenic accumulated by corn seedlings using XAS and DRC-ICP-MS

ICP-MS was used to investigate the uptake of As(III) and As(V) from hydroponics growth media by corn seedlings. It was found that arsenic uptake by the plant roots for the arsenic(V) and arsenic(III) treatments were 95 and 112 ppm, respectively. However, in the shoots of the arsenic (V) treatments had 18 ppm whereas arsenic(III) treatments had 12 ppm. XANES studies showed that As for both treatments arsenic was present as a mixture of an As(III) sulfur complex and an As(V) oxygen complex. The XANES data was corroborated by the EXAFS studies showing the presence of both oxygen and sulfur ligands coordinated to the arsenic. Iron concentrations were found to increase by 4 fold in the As(V) contaminated growth media and 7 fold in the As(III) treatment compared to the control iron concentration of 500 ppm. Whereas, the total iron concentration in the shoots was found to decrease by approximately the same amount for both treatments from 360 ppm in the control to approximately 125 ppm in both arsenic treatments. Phosphorus concentrations were found to decrease in both the roots and shoots compared to the control plants. The total sulfur in the roots was found to increase in the arsenic(III) and arsenic(V) treatments to 560 ppm and 800 ppm, respectively, compared to the control plants 358 ppm. In addition, the total sulfur in shoots of the plants was found to remain relatively constant at approximately 1080 ppm. The potassium concentrations in the plants were found to increase in the roots and decrease in the shoots.     

Effect of mixed cadmium,copper, nickel and zinc at different pHs upon alfalfa growth and heavy metal uptake

Alfalfa plants were grown in soil-pots contaminated with a mixture of Cd(II), Cu(II), Ni(II), and Zn(II), (at 50 mg/kg each) at pHs of 4.5, 5.8, and 7.1. The plants were fertilized using a nutrient solution, which was adjusted appropriately to the same pH. Plants in the control treatment were grown in the absence of the heavy metals mixture. The growth of the control plants was the same at the three pHs studied and the heavy metal stressed plants also showed similar behavior at each pHs. There were statistically significant differences (P<0.05) between the shoot length of the control treatment plants and the length of plants grown in the presence of the heavy metal mixture. Under the effects of the heavy metal mixture, nickel was the most accumulated element in the shoot tissue, with 437, 333, and 308 ppm at pH 7.1, 5.8, and 4.5, respectively. Cadmium was found to be second in accumulated concentrations with 202 ppm, 124 ppm, and 132 ppm at pH 7.1, 5.8, and 4.5, respectively, while zinc was third, followed by copper. The maximum relative uptakes (element in plant/element in soil-water-solution) were found to be 26 times for nickel, 23 times for cadmium, 12 times for zinc. and 6 times for copper. We considered these relations as indicative of the ability of alfalfa plants to take up elements from a soil matrix contaminated with a mixture of cadmium, copper, nickel, and zinc.     

Sorption of hazardous metals from single and multi-element solutions by saltbush biomass in batch and continuous mode: interference of calcium and magnesium in batch mode

Batch studies were performed to determine the interference of calcium (Ca) and magnesium (Mg) on the sorption of Cu(II), Cd(II), Cr(III), Cr(VI), Pb(II), and Zn(II) [from CuSO(4), K(2)Cr(2)O(7), Pb(NO(3))(2), Cr(NO(3))(3), ZnCl(2), and Cd(NO(3))(2)] by saltbush (Atriplex canescens) biomass. The results demonstrated that Ca and Mg at concentrations of at least 20 times higher than the concentration of most of the target metals did not interfere with the metal binding. The data show that the batch binding capacity from a multimetal solution at pH 5.0 was (micromol/g) about 260 for Cr(III) and Pb, and about 117, 54, and 49 for Cu, Zn, and Cd, respectively. The use of 0.1M HCl allowed the recovery of 85-100% of the bound Cu, Cr(III), and Pb, and more than 37% of the bound Cd and Zn. The column binding capacity for Pb was about 49 micromol/g from both the single and multimetal solutions, while it was, respectively about 35 and 23 micromol/g for Cr(III). The binding capacity for Cu and Zn from the single and multimetal column experiments was 35 micromol/g and less than 10 micromol/g, respectively. The stripping data from the single column experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and Zn, 90% and 74% of the bound Pb and Cr(VI), respectively, and less than 25% of the bound Cd and Cr(III), while the stripping from the multimetal experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and about 74%, 54%, 43%, and 40% of the bound Pb, Zn, Cd, and Cr(III), respectively.     

Enhancement of lead uptake by alfalfa (Medicago sativa) using EDTA and a plant growth promoter

Phytoremediation is a novel cleanup technology for the removal of contaminants from polluted waters and soils. In phytoremediation, the plant uptake capability and the availability of the pollutant in the media are important. Here we show the results of a study on the combined effects of ethylenediaminetetraacetic acid (EDTA) and the phytohormone indole-3-acetic acid (IAA) on Pb uptake by Medicago sativa (alfalfa). Plants were grown in hydroponics media containing a nutrient solution amended with Pb at 0.2mM and different combinations of EDTA, and IAA. After 10d of treatment, the Pb content in plant tissues was quantified using an Inductively Coupled Plasma Optical Emission Spectrometer (ICP/OES). The results showed that the combination of 100 microM IAA/0.2 mM EDTA increased the Pb accumulation in leaves by about 2800% and by about 600%, as compared to Pb content in leaves of plants exposed to Pb alone and those cultivated with Pb/EDTA, respectively. These results indicate that non-metal hyperaccumulator plants could increase their hyperaccumulating potential without genetic manipulation.