MULTICOMPONENT GEOCHEMICAL TRANSPORT MODELING USING HYDRUS-1D AND HP11

Abstract: The transport of reactive contaminants in the subsurface is generally affected by a large number of nonlinear and often interactive physical, chemical, and biological processes. Simulating these processes requires a comprehensive reactive transport code that couples the physical processes of water flow and advective-dispersive transport with a range of biogeochemical processes. Two recently developed coupled geochemical models that are both based on the HYDRUS-1D software package for variably saturated flow and transport are summarized in this paper. One model resulted from coupling HYDRUS-1D with the UNSATCHEM module. While restricted to major ion chemistry, this program enables quantitative predictions of such problems as analyzing the effects of salinity on plant growth and the amount of water and amendments required to reclaim salt-affected soil profiles. The second model, HPI, resulted from coupling HYDRUS-1D with the PHREEQC biogeochemical code. The latter program accounts for a wide range of instantaneous or kinetic chemical and biological reactions, including complexation, cation exchange, surface complexation, precipitation dissolution and/or redox reactions. The versatility of HP1 is illustrated in this paper by means of two examples: the leaching of toxic trace elements and the transport of the explosive TNT and its degradation products.     

USE OF X-RAY FLUORESCENCE TO DETERMINE TRACE METALS IN WATER RESOURCES1

ABSTRACT. The X-ray fluorescence method was used to analyze trace metals collected in particulate form on filter papers and from the ionic state by ion exchange filter papers. The samples were prepared by allowing water to pass through these filter papers. The procedures necessary for using the X-ray fluorescence method are described. A number of samples were taken from the Great Miami River in Dayton, Ohio over one year showing the presence of the following metals, Ca, Ti, Cr, Fe, Cu, Zn, Sr, and Cd. Elements in the periodic table between Ti and Cs were detectable to a sensitivity limit of the order of 30 ppb for metals in the particulate form and 0.4 ppm for metals in the ionic form.     

Distribution of Trace Metals in the Surface Sediments of Two Pristine Subalpine Lakes in Taiwan

Sediment cores were collected from two remote subalpine lakes: the rather shallow (1.5 m) Little Ghost Lake at 2040 m elevation and the deeper, Great Ghost Lake (40 m) at 2150 m elevation. Different early diagenesis of metals were observed. the seasonally anoxic hypolimnion drives the annual iron redox cycle and causes the remobilization of metals in the mobile fractions of sediments in the Great Ghost Lake. These result in the redistribution of metals in the mobile fractions of sediment and poor correlation between metal concentrations. in the Little Ghost Lake, the shallow water column is always oxic with less change of metals in the mobile fractions of sediments. As a result, most metals have strong positive correlations with each other.

The distributions of metal/Al ratios, total metal contents and acid-leached metal concentrations in the near-surface sediments of these two lakes suggest that the anthropogenic inputs from the atmospheric fallouts in recent decades are one of the major factors affecting the distributions of metals such as cadmium, lead and, to a lessor extent, zinc. the Pb-206/Pb-207 ratios confirm the anthropogenic lead input in these surface sediments.     

Toxicities and tolerances of Cd, Cu, Pb and Zn in a primary producer (Isochrysis galbana) and in a primary consumer (Perna viridis)

Studies on toxicities and tolerances of cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) in the brown alga Isochrysis galbana and in the green-lipped mussel Perna viridis were conducted by short-term bioassays using endpoints growth production and mortality, respectively. The 5-day EC(50) and 24-h LC(50) of these heavy metals were determined in the brown alga and mussel, respectively. The EC(50) values calculated for the alga were 0.74 mg/l for Cd, 0.91 mg/l for Cu, 1.40 mg/l for Pb and 0.60 mg/l for Zn. The LC(50) values for the mussels were 1.53 mg/l for Cd, 0.25 mg/l for Cu, 4.12 mg/l for Pb and 3.20 mg/l for Zn. These LC(50) values were within the concentration ranges as reported by other authors who used P. viridis as the test organism. Based on these EC(50) and LC(50) values, the alga was most sensitive to Zn, followed by Cd, Cu and Pb while the mussel was most sensitive to Cu, followed by Cd, Zn and Pb. Differences in the trophic levels, metal handling strategies, biology and ecology of the primary producer (brown alga) and the primary consumer (mussel) are believed to be the plausible causes for the different toxicities and tolerances of the metals studied.     

Monitoring environmental pollution in Erzurum by chemical analysis of Scots pine (Pinus sylvestris L.) needles

Pollution distribution maps of copper (Cu), zinc (Zn) and lead (Pb) for Erzurum province were developed on the basis of chemical analysis of Scots pine (Pinus sylvestris L.) needles collected from randomly selected sampling points during 2 years. The maps show deposition zones for the studied elements and could help in identification of sources and directions of air pollution dispersion. This study indicated that vegetation in Erzurum was greatly endangered by sulphur dioxide (SO(2)), whereas Zn does not pose an immediate threat to vegetation in most of the country's territory. However, in the city center, main and secondary road agglomeration, very high pollution with Pb and Cu could limit growth. Higher levels of SO(2) measured in some areas of Erzurum might be harmful for human and animal health. Results of this study indicated that Scots pine needles were not contaminated by Zn.     

Assessment of contamination by heavy metals and petroleum hydrocarbons in sediments of Montevideo Harbour (Uruguay)

As part of the first environmental assessment within Montevideo Harbour, in summer and winter of 1998, sediments samples were collected at eight locations to determine the spatial distribution of anthropogenic pollutants. Muddy sediments with high organic matter content dominate the study area. Heavy metal levels indicated that sediments were highly polluted with Zn (overall mean: 312+/-102 microg g(-1) dry sediment), Pb (85+/-31), Cu (89+/-25), Cr (162+/-62), and Hg (0.63+/-0.3) and moderately with Ni (30+/-2) and Ag (1.2+/-0.4). Depending on location and season, aliphatic hydrocarbons reached from 21 to 120 microg g(-1), while the unresolved complex mixture represented up to 76% of the total aliphatic fraction. Total PAH concentrations ranged from 1.56 to 90.44 microg g(-1); except at one location, petroleum derivatives were identified as main local source. The results pointed out that almost all the harbour area presented some substances that can cause adverse biological effects, especially in the inner region where all metals are above PEL levels. Principal components analysis confirmed that the inner harbour region is most severely affected by the pollutants and it was possible to differentiate three regions according to their environmental quality.     

Bioremediation of Chromate by Sulfate-Reducing Bacteria, Cytochromes c3 and hydrogenases

The treatment of soils and ground waters polluted by heavy metals is of economical and environmental interest. Reduction of Cr(VI) to the less toxic Cr(III) associated to its precipitation is a potentially useful process for bioremediation. In order to develop ecological processes using micro-organisms, we have compared various sulfate-reducing bacteria for enzymatic reduction of chromate. The best Cr(VI) reductase activity was obtained with Desulfomicrobium norvegicum. Despite morphological changes induced by the presence of chromate, this strain can grow in the presence of up to 500 M Cr(VI) and can decontaminate waters polluted by Cr(VI) when seeded in bioreactors. We have demonstrated the ability of several metalloenzymes (cytochromes c ₃ and hydrogenases) to reduce chromate. Biophysical investigations of the chromate/protein interaction in order to get further informations on the mechanism of metal reduction by cytochromes c ₃ are under the way.     

Study of Trace and Heavy Metals in Rural and Urban Aerosols of Uludağ and Bursa (Turkey)

The concentrations of heavy, trace elements and major ions measuredin the Uluda and Bursa aerosols were investigated to assess size distributions, spatial and temporal variability, sources and source regions affecting the composition of aerosols in Uluda and Bursa. A total of 81 samples were collected in two sites, one in Bursa city and another in the Uluda Mountain during two sampling campaigns. Daily samples were collected using a high volume sampler on Whatman 41 cellulose filters in Uluda, while three days interval samples were collected in Bursa using an automatic dichotomous sampler on PTFE Teflon filters. Samples were analysed for 15 trace and heavy metals (Al, Fe, Ba, Na, Mg, K, Mn, Ca, Cu), (V, Pb, Cd, Cr, Ni, Zn), and 4 major ions (SO₄ ^2-, NO₃ ^-, Cl^-), (NH₄ ⁺) using ICP-AES, GFAAS, HPLC and UV/VIS Spectrophotometer,respectively. In general, concentrations of the metals measured inUluda aerosols were lower than those in Bursa. The concentrations of crustal elements were higher in summer than winter, while anthropogenic elements had higher concentrations in winter than summer. Most of the mass of crustal elements was concentrated in the coarse mode while the mass of the heavy metals was concentrated in the fine mode. Factor analysis revealed four factors with sources including crustal, industrial and combustion. Back trajectory calculations were used to determine long range contributions. These calculations showed that contributions were mostly from European countries, former Soviet Union countries, Black Sea and North Africa.     

Sediment and porewater geochemistry in a metal contaminated estuary,Dulas Bay,Anglesey

Remobilisation of contaminant metals from sediments can occur by chemical, biological or physical changes. This in turn can lead to contaminant fluxes to the porewaters and ultimately the water column. The aim of the research presented here is to document post-depositional controls on metal mobility and fluxes in a heavily metal-contaminated estuary. This will allow for an improved understanding of the impact of contaminated sediments on water quality from both a short-term and long-term perspective. Dulas Bay is situated on the east coast of Anglesey, North Wales, and receives polluted waters from Parys Mountain. Metals within Dulas Bay sediments show surface enrichment and variations in mineralogical form. Diagenesis clearly plays a role in post-depositional behaviour of the metals, forming sulphides and potentially carbonates. The presence of a dominant exchangeable/carbonate fraction, and elevated porewater metals, in this sulphidic system is significant and could indicate the presence of freshwater diagenesis, or, reflect the high levels of metals in the sediment.     

Heavy Metals in Stockholm Groundwater – Concentrations and Fluxes

Sampling of groundwater in theQuaternary deposits was carried out at 70 sitesin Stockholm for, among other things, metalanalyses. The objectives were to get a notion of the metal content and to get a basis for anestimation of the order of magnitude of thegroundwater transported metal contribution to themain surface water bodies in comparison to otherroutes. Thus, in three watershed areaswithin the Stockholm Town, groundwater flow andmetal concentration propagation were simulatedand metal fluxes were calculated. Theconcentrations of heavy metals were in generalfound to be very high in comparison withgroundwater in forested areas. This was mostpronounced for mercury (Hg) and copper (Cu). Themost remarkable result was a Hg concentration of4.57 g L^-1 in the vicinity of a closed downhospital. The annual contribution of heavy metals(kg) by groundwater to the main surface waterbodies was estimated to: As (2.2), Cd (0.20), Co(4.9), Cr (3.1), Cu (34), Hg (0.06), Ni (28), Pb(2.2) Zn (118). These fluxes are much smallerthan those in forest ecosystems, due to lowergroundwater recharge in urban areas, where agreat part of the runoff is diverted bylandsealing, drainage, tunnels etc. The modelingresults emphasize the importance of the sorptionprocesses indicating that the modeled areas arein a non-steady state condition. It also showsthat the sources generating elevatedconcentrations of the high adsorptive metals Pband Hg are likely to be nearby.