Irreversible sorption of pentachlorophenol to sediments: experimental observations

The partitioning behavior of pentachlorophenol (PCP) in five sediments was studied using equilibrium sorption experiments and multiple cycles of sorption and desorption experiments. The results of the equilibrium sorption experiments showed that the isotherms of PCP on five sediments were linear and the partitioning coefficients (Kd) were proportional to the organic carbon content of the sediments. The average organic carbon content normalized partitioning coefficient (logK oc) of five sediments was 2.83 +/- 1.48. In multiple cycles of sorption and desorption experiments, the five sediments were found to exhibit statistically significant sorption-desorption hysteresis, and the hysteresis indices (HI) varied over a wide range (0.72 - 11.82). Correlations between the HI value and the percentage of lipid in the total organic matter in the sediment indicated that lipid was the main fraction to affect the hysteresis phenomenon, i.e., the higher the lipid percentage the greater the HI value. The hysteresis phenomenon was mostly caused by irreversible sorption of PCP on lipids, including entrapment by lipids, which induced the slow desorption rate from the sediment. Because of hysteresis in the sorption and desorption, the PCP ecological toxicity would be lower than expected.     

Association of organic matter, iron and inorganic phosphorus in lake waters

Gel permeation chromatography was used to fractionate ³²PO₄³⁻ labelled components by molecular size in filtered, destabilized lake foam, concentrated lake water, and lake sediment extracts. Evidence is presented for the abiotic formation of organic matter iron inorganic P complexes in lake foam, water and sediments. ³²PO₄^staggered was found to excahnge with low molecular weight, dissolved P fraction, probably an organic matter -Fe- inorganic P complex, but not with a high molecular weight, non-inorganic dissolved reactive P pool, hypothesized to be similar to the dimer. Our experiments suggest that inorganic P binding by high molecular weight organic matter may play a significant role in the P cycle. If the bound P is unavailable to algae and bacteria, the complexes could explain Rigler's (1968) hypothesis that the molybdenum blue technique may overestimate the free orthophosphate concentration by 10–100 times.     

Residue of pentachlorophenol in freshwater sediments and human breast milk collected from the Pearl River Delta, China

Pentachlorophenol (PCP) was investigated in freshwater sediments and human breast milk collected from the Pearl River Delta, China. The average level of PCP in river sediments was 7.93 ng/g based on dry weight, ranging from 1.44 to 34.4 ng/g. As to the sediments from fishponds, samples from Zhongshan had the highest PCP levels (37.5 ng/g on average), followed by Dongguan (21.1 ng/g on average) and the least in Shenzhen (3.69 ng/g on average) and Shunde (2.20 ng/g on average). Negative relationship was obtained between the PCP level and pH value in sediment (r=0.553, n=13, p<0.05), while positive relationship was found between the PCP levels and the total organic matter (TOM) levels in sediment (r=0.700, n=17, p<0.01). These results indicated that pH and TOM played important roles during the process of PCP settling down to the sediment. PCP was also detected in human breast milk with an average of 2.15 ng/g. The PCP concentration increased with the age increasing of donors. The estimated PCP body burden for mother, daily and yearly PCP intake of infants ranged from 0.16 to 4.17 mg/person, from 0.26 to 10.23 mug/infant.day and from 0.09 to 3.73 mg/infant.year, respectively.     

Sorption of metals onto natural organic matter as a function of complexation and adsorbent-adsorbate contact mode

The effect of complexing anion and adsorbate-adsorbent contact mode (static equilibrium or dynamic non-equilibrium) on binding and partition of Cu(2+), Cd(2+) and Zn(2+) onto organic matter (exemplified in a low-moor peat) was studied. The study comprised comparative batch and column flow-through sorption experiments on monometallic solutions of Me-Cl and Me-SO(4) salts, at pH 4.0, and sequential fractionation of sorbed metals with respect to binding strength. Both the presence of an anion having complexing properties (Cl(-)) as well as a contact mode was found to quantitatively and qualitatively affect the sorption capacity and binding strength of organic matter (peat) for metal ions. Complexing effect of Cl(-) on metal ions resulted mostly in reduction of metal ability to form strongly bound metal-organic compounds, in accordance with the order of stability constant of complex ions log K: Cd>Zn>Cu. Flow-through (dynamic) contact mode, which is the most appropriate to simulate environmental conditions, appeared to strongly attenuate the complexing effect of chloride ions on Cd and Zn sorption, and significantly enhance sorption capacity also in the absence of complexing ions. For Cd, it was mainly due to the enrichment in the strongly bound "insoluble organic" fraction, while for Zn the quantitative increase of sorption capacity did not alter significantly its partitioning. Neither a quantitative nor qualitative effect of contact mode on Cu binding was observed. Complex and diverse effects of different environmental parameters on metal sorption capacity and binding strength onto organic matter, which strongly influence metal mobility, leads to the conclusion that the correct simulation of these parameters for ecotoxicological testing is crucial for the reliable predicting of metal bioavailability under actual terrestrial environmental conditions.     

巢湖及其入湖河流（南淝河）沉积物磷形态与吸附行为的垂直变化

沉积物磷释放可明显促进水体富营养化,但其关键组分与调控因素尚待深入研究。系统分析了巢湖及其入湖河流（南淝河）沉积物有机质(OM)、不同形态磷含量、磷吸附参数的垂直分布特征。结果表明：铁结合态磷(Fe(OOH)~P)与钙结合态磷(CaCO3~P)为沉积物磷的主要存在形态,且均与磷平衡浓度（EPC0）显著正相关。与巢湖相比,南淝河具有明显较高的沉积物最大磷吸附量（Qmax）,而由此增强的磷缓冲能力可被较高的Fe(OOH)~P含量所抵消,从而表现出较强的磷释放潜力（高EPC0值）。有机质能以线性方式增加Fe(OOH)~P、CaCO3~P与Qmax,并据此调节EPC0。南淝河沉积物亚表层（10～15 cm）显示EPC0的最小值,从而具有相对较小的磷释放风险     

Occurrence and behaviour of radionuclides in the Moselle River-Part II: Distribution of radionuclides between aqueous phase and suspended matter

Most of the radionuclides released from nuclear power plants ( NPPs) into rivers are primarily adsorbed onto suspended matter. To describe this nuclide transfer, a model was used which takes the total suspended matter load as solid phase into account. The necessary partition factors of various radionuclides were determined in river water/suspended matter of the Moselle in laboratory investigations. By use of this model, a conservative estimate of the radionuclide concentration of the solid phase could be obtained which proved to be more realistic than the results based on the distribution law.Furthermore, the influence of grain-size on the specific activity of single fractions of a Moselle sediment was demonstrated using ¹³⁷Cs, ¹⁰⁶Ru and ¹⁴⁴Ce from the Chernobyl nuclear accident as tracers. The grain-size pattern is considered to be a main factor which may seriously distort the determination of distribution coefficients and concentration factors that are needed in applying the model based on the distribution law.     

Biological vs. chemical properties of natural organic matter isolated from selected Norwegian lakes

Relationships among different spectroscopic, chemical, and biological properties of dissolved natural organic matter (NOM) were investigated. NOM samples were isolated by means of reverse osmosis from eight Norwegian lakes. Elemental composition, absorption spectra (UV, VIS, IR), the influence on algal growth, and accumulation rates of metals by mussels in the presence of NOM were measured. Linear regression and principal components analyses were utilised to assess relationships between the biological and chemical properties. It was concluded that the content of organic matter in the isolates and the aromaticity of NOM, as characterised by UV and VIS spectra, are best correlated with the biological properties.     

消浪工程对太湖底泥再悬浮及营养盐释放的影响

为了解863消浪工程对太湖底泥再悬浮及营养盐释放的抑制作用,于2005年7月15～17日在工程区投放悬浮物捕获器测定沉积物的再悬浮通量,并分层采集水样进行水体营养盐浓度的垂向分布研究。16日平均风速3 m/s时,测得的再悬浮通量上层最大值为7.22 g/d·m2,下层最大值为41.8 g/d·m2;17日平均风速5 m/s时,测得的再悬浮通量上层最小值24.7 g/d·m2,下层最小值为48.4 g/d·m2,沉积物再悬浮通量与风浪扰动强度关系密切。对比消浪工程区内外沉积物的再悬浮通量表明,消浪工程能够显著减弱风浪对底泥的扰动,抑制沉积物再悬浮,减轻营养盐的内源释放通量。实验结果还表明,太湖水体悬浮物浓度越高,悬浮物的有机质含量就越低,相应地,单位悬浮物中磷的含量也越低。随着风浪扰动的持续和增强,尽管能够将更多的沉积物间隙水中的溶解性磷带入水体,但是,野外观测中发现水体溶解性的磷含量并未相应增高甚至降低,这可能是由于水体中悬浮物浓度越高,对水体溶解性磷的吸附能力也越高,从而使得水中溶解性磷的含量增高不显著甚至降低。     

Modelling the physico-chemical speciation of plutonium in the eastern Irish Sea: a further development

A numerical full three-dimensional model previously developed to simulate the physicochemical speciation of plutonium in the eastern Irish Sea has been improved. The model solves simultaneously the hydrodynamic equations, the suspended matter equation and the equations that give the time evolution of Pu concentrations in water, suspended matter and bottom sediments. It is considered that Pu may exist in each phase in two different oxidation states. Redox reactions are also considered. In the earlier version of the model, a one-step kinetic model was used to describe the transfers of radionuclides between the dissolved and solid phases. Although with this kind of model the contamination of the sediments can be properly simulated, it is clearly not able to describe the re-dissolution of radionuclides from a contaminated sediment once the external source to the sea is reduced. Thus, the model has been improved by substituting the one-step model with a two-step kinetic model consisting of two consecutive reversible reactions. Now it is possible to simulate both the sediment contamination and the re-dissolution processes.     

Effects of changing land use on dissolved organic matter in a subtropical river watershed, southeast China

The composition of dissolved organic matter (DOM) is an important determinant for its biogeochemical role in the aquatic environments. Therefore, it is crucial to determine the effects of changing land use on the DOM composition in the river watershed. Water samples were collected from the outlets of 15 sub-watersheds in the subtropical Jiulong River (southeast China) for fluorescence measurements and parallel factor analysis. Two humic-like (C1 and C2) and one protein-like (C3) fluorescent components were identified. Overall, DOM in the Jiulong River watershed was dominated by humic-like materials, probably due to the fact that 69% of the watershed is covered with forest. The 15 sub-watersheds were grouped into four clusters based on the proportion of each fluorescent component in the total fluorescence, suggesting that the DOM composition could be very different among sub-watersheds. There was a strong negative correlation between C2 and C3%. C1% correlated with the water body fraction, likely associated with the aquatic production of C1. C3% correlated positively with the residential area fraction, likely indicating the influence of anthropogenic activities. These results are useful for assessing the effects of land use/land cover changes on the composition and hence biogeochemical roles of DOM in aquatic environments.     

Speciation and hydrological transport of metals in non-acidic river systems of the Lake Baikal basin: Field data and model predictions

The speciation of metals in aqueous systems is central to understanding their mobility, bioavailability, toxicity and fate. Although several geochemical speciation models exist for metals, the equilibrium conditions assumed by many of them may not prevail in field-scale hydrological systems with flowing water. Furthermore, the dominant processes and/or process rates in non-acidic systems might differ from well-studied acidic systems. We here aim to increase knowledge on geochemical processes controlling speciation and transport of metals under non-acidic river conditions. Specifically, we evaluate the predictive capacity of a speciation model to novel measurements of multiple metals and their partitioning, under high-pH conditions in mining zones within the Lake Baikal basin. The mining zones are potential hotspots for increasing metal loads to downstream river systems. Metals released from such upstream regions may be transported all the way to Lake Baikal, where increasing metal contamination of sediments and biota has been reported. Our results show clear agreement between speciation predictions and field measurements of Fe, V, Pb and Zn, suggesting that the partitioning of these metals mainly was governed by equilibrium geochemistry under the studied conditions. Systematic over-predictions of dissolved Cr, Cu and Mo by the model were observed, which might be corrected by improving the adsorption database for hydroxyapatite because that mineral likely controls the solubility of these metals. Additionally, metal complexation by dissolved organic matter is a key parameter that needs continued monitoring in the Lake Baikal basin because dependable predictions could not be made without considering its variability. Finally, our investigation indicates that further model development is needed for accurate As speciation predictions under non-acidic conditions, which is crucial for improved health risk assessments on this contaminant.

     

溪洛渡水电工程拦沙对三峡水库富营养化潜在影响的初步研究

从泥沙吸附的角度，探讨金沙江溪洛渡水电站拦沙对三峡水库溶解性磷负荷的影响。2006年11月在金沙江、长江干流和支流岷江、沱江采集了淤积泥沙和水样，测定了泥沙的全磷、有效磷和磷固定量及水的溶解性磷等指标。岷江和沱江泥沙的有效磷含量远高于金沙江和长江干流，反映了四川盆地支流的磷污染较干流严重；干流泥沙的有效磷含量向下游呈增加和磷固定量向下游呈减少的趋势，反映了干流泥沙沿途不断吸附四川盆地支流汇入干流中的溶解性磷，磷固定能力有所降低。根据金沙江宜宾与长江朱沱泥沙的有效磷含量和磷固定量，金沙江来沙年吸附溶解性磷分别为382和6 885 t，分别相当于朱沱站的26%和468％。溪洛渡水库拦蓄泥沙，金沙江来沙吸附长江干流溶解性磷的量将有所减少。水库投入运行后的前50年，以有效磷含量计，金沙江来沙的磷吸附量占朱沱年溶解性磷总量的比例从26%降至10%；以磷固定量计，从468％降至174%。长江干流进入三峡水库的年溶解性磷总量有可能增加16%～294%。金沙江来沙降低三峡入库磷负荷的实际功能，可能介于有效磷含量和磷固定量的计算值之间，具体值还需开展进一步的试验研究。     

Distribution of tritium in estuarine waters: the role of organic matter

Tritium is an important environmental radionuclide whose reactivity with ligands and solids in aquatic systems is assumed to be limited. We studied the fractionation and sorption of tritium (added as tritiated water) in river water and seawater, and found that its distribution appears to be influenced by its affinity for organic matter. Tritium rapidly equilibrates with dissolved organic ligands that are retained by a reverse-phase C18 column, and with suspended sediment particles. Significantly, a measurable fraction of sorbed tritium associates with proteinaceous material that is potentially available to sediment-feeding organisms. These characteristics have not been reported previously and cannot be accounted for solely by isotopic exchange with hydrogen. Nevertheless, they are in qualitative agreement with available measurements of tritium in estuarine and coastal waters where its principal discharge is as tritiated water. Further research into the estuarine biogeochemical behaviour of tritium is required and radiological distribution coefficients and concentration factors that are assumed for this radionuclide may require reconsideration.     

Derivation of predicted no effect concentrations (PNEC) for marine environmental risk assessment: application of different approaches to the model contaminant Linear Alkylbenzene Sulphonates (LAS) in a site-specific environment

Four sediment-dwelling marine organisms were exposed to sediments spiked with increasing concentrations of Linear Alkylbenzene Sulphonate (LAS). The selected endpoint mortality was reported daily and acute LC(50) (96 h), as well as final LC(10) values were calculated for the derivation of environmentally safe predicted no effect concentrations (PNEC) for the sediment compartment. PNECs were estimated by both application of assessment factors (AF) and the equilibrium partitioning method (EPM) as proposed by the EU TGD. Finally, environmental risk assessment in a site-specific environment, the Sancti Petri Channel, South Iberian Peninsula, was carried out at three different sampling stations with known environmental LAS concentrations. PNECs obtained by the assessment factor approach with acute toxicity data were one to two orders of magnitude lower than those from the equilibrium partitioning method. On the other hand, when applying lower AFs to the estimated LC(10) values, the PNECs obtained by both approaches were more similar. Environmental risk assessment carried out with the estimated PNECs in a site specific environment with known sediment LAS concentrations revealed that PNECs obtained with acute toxicity data were over conservative whereas those obtained with AF=10 on LC(10) data and EPM produced more realistic results in accordance with field observations carried out in the study area.     

Partition of iodine (¹²⁹I and ¹²⁷I) isotopes in soils and marine sediments

Natural organic matter, such as humic and fulvic acids and humin, plays a key role in determining the fate and mobility of radioiodine in soil and sediments. The radioisotope ¹²⁹I is continuously produced and released from nuclear fuel reprocessing plants, and as a biophilic element, its environmental mobility is strongly linked to organic matter.Due to its long half-life (15.7 million years), ¹²⁹I builds up in the environment and can be traced since the beginning of the nuclear era in reservoirs such as soils and marine sediments. Nevertheless, partition of the isotope between the different types of organic matter in soil and sediment is rarely explored. Here we present a sequential extraction of ¹²⁹I and ¹²⁷I chemical forms encountered in a Danish soil, a soil reference material (IAEA-375), an anoxic marine sediment from Southern Norway and an oxic sediment from the Barents Sea. The different forms of iodine are related to water soluble, exchangeable, carbonates, oxides as well as iodine bound to humic acid, fulvic acid and to humin and minerals. This is the first study to identify ¹²⁹I in humic and fulvic acid and humin. The results show that 30-56% of the total ¹²⁷I and 42-60% of the total ¹²⁹I are associated with organic matter in soil and sediment samples. At a soil/sediment pH below 5.0-5.5, ¹²⁷I and ¹²⁹I in the organic fraction associate primarily with the humic acid while at soil/sediment pH > 6 ¹²⁹I was mostly found to be bound to fulvic acid. Anoxic conditions seem to increase the mobility and availability of iodine compared to oxic, while subaerial conditions (soils) reduces the availability of water soluble fraction compared to subaqueous (marine) conditions.     

典型城内过富营养湖泊沉积物和间隙水中各形态磷的相关性研究

研究了武汉市繁华市中心典型过富营养湖泊沉积物—间隙水体系磷形态的相关性。对沉积物—间隙水中磷形态的连续提取分析发现,自然粒度下,沉积物中有机质含量与沉积物中有机/细菌聚合磷存在很好的线性相关性,说明沉积物中有机质是有机/细菌聚合磷的源;沉积物中总磷决定间隙水中总溶解性磷和溶解性磷酸盐的含量,并且总磷与间隙水中总溶解性磷和溶解性磷酸盐存在很好的相关性;沉积物中Fe P和Al P分别与间隙水中的Eh和溶解性磷酸盐存在相关性,说明Eh的大小严重影响Fe P和Al P的含量,但是Fe P和Al P含量之和又主导着间隙水中溶解性磷酸盐的含量。对典型市内过富营养湖泊的沉积物－间隙水体系中形态磷的相关性研究,旨在为控制这种典型过富营养湖泊沉积物中磷向水体释放提供理论参考。     

Effects of dissolved organic matter on toxicity and bioavailability of copper for lettuce sprouts

It is well known that dissolved organic matter in soil solution may affect the toxicity or bioavailability of heavy metals to plants, but existing information on various organic substances is insufficient for treating problems with heavy metal-contaminated soils. To clarify how dissolved organic matter alters the toxicity and bioavailability of metals, we germinated lettuce seeds exposed to solutions containing Cu and several kinds of dissolved organic matters. Low molecular weight organic acids (citric, malic, and oxalic acids) increased the toxicity and bioavailability of Cu, but low concentrations of the synthetic chelators ethylenediamine tetra-acetic acid (EDTA) and diethylenetriamine penta-acetic acid (DTPA) decreased the toxicity and bioavailability of Cu. In contrast, humic acid appeared to be the most effective organic substance for detoxifying Cu, even though it did not significantly decrease the bioavailability of Cu. Consequently, the bioavailability and toxic effects of Cu in soil depend on the nature of coexisting organic substances in the soil solution.     

The use of ultra filtration in trace metal speciation studies in sea water

During this work, size fractionation technique "ultra filtration" is used in speciation studies of trace elements in the coastal sea water. Filtration is the most commonly used method to fractionate trace metal species, but often only "dissolved" and "particulate" fraction. The purpose of the present study is to determine colloidal and suspended particulate concentrations of Fe, Zn, Cu, Ni, and Mn in sea water. Suspended particulate matter were separated in three different size groups namely (>2.7 microm, <2.7->0.45 microm and <0.45->0.22 microm) by suction filtration using cellulose acetate and nitrate filter membranes. Thereafter to concentrate the solution with colloidal particle <0.22 microm-1.1 nm (0.5 k Nominal Molecular Weight cut-off Limit {NMWL}), the solution obtained from filtration through <0.22 microm, is sequentially passed through the ultra-filtration membranes having pore diameters of 14 nm (300 k NMWL), 3.1 nm (50 k NMWL), 2.2 nm (30 k NMWL), 1.6 nm (10 k NMWL) and 1.1 nm (0.5 k NMWL) by using Stirred Ultra-filtration Cells, operating in concentration mode. The concentration of Fe, Zn, Cu, Ni, and Mn were measured in suspended and dissolved fraction by ion chromatography, ICP-AES and Atomic Absorption Spectrometer. The salinity of the solution in various dissolved fractions of sequential filtration varies between 30.89-34.22 parts per thousand. The maximum concentrations of colloidal Zn, Cu, Ni and Mn in dissolved fraction were in <2.2->1.6 nm fraction. In case of Fe, colloidal fractions <2.2->1.6 nm and <1.6-<1.1 nm shows higher concentration. The concentration of Zn, Cu, Ni and Mn increase with decrease in size in suspended particulate matter, while the reverse is observed in case of Fe. This size separation data that specifies the partitioning of metals between dissolved and suspended solid phases is necessary for developing physically based models of metal transport in aquatic system.     

A follow up of the decrease of non exchangeable organically bound tritium levels in the surroundings of a nuclear research center

In the past decades limited amounts of tritium were handled on the CEA site of Bruyères le Châtel with authorised atmospheric releases. A small fraction of the tritium released entered into environmental samples under three forms: (i) as part of free water (TFWT - Tissue Free Water Tritium), or associated with organic matter in two ways; either (ii) bound to the oxygen and nitrogen atoms of the material as exchangeable organically bound tritium (E-OBT), or (iii) bound to carbon atoms as non exchangeable organically bound tritium (NE-OBT). The first two components provide only a picture of atmospheric tritium concentrations at the sampling time as they are in equilibrium with atmospheric moisture and soil humidity. Unlike these exchangeable forms, however, NE-OBT is tightly bound to the organic matter and provides an integrated record of atmospheric tritium during the growing phase of the vegetation. We mapped NE-OBT in tree leaf samples in an area of about 25 × 30 km² around the centre of the CEA site and compared the results with those obtained during a previous sampling exercise in 1989. At this time, the activity levels were almost ten times higher than those observed presently in a similar area almost 20 years later which is consistent with the decrease of atmospheric releases issued from the centre. As the activity levels are now close to environmental background specific attention was also paid to the analytical procedure to ensure reliable low level NE-OBT detection.     

Correlation of the partitioning of dissolved organic matter fractions with the desorption of Cd,Cu, Ni,Pb and Zn from 18 Dutch soils

Eighteen Dutch soils were extracted in aqueous solutions at varying pH. Extracts were analyzed for Cd, Cu, Ni, Pb and Zn by ICP-AES. Extract dissolved organic carbon (DOC) was also concentrated onto a macroreticular resin and fractionation into three operationally defined fractions: hydrophilic acids (Hyd), humic acids (HA) and fulvic acids (FA). In this manner, change in absolute solution concentration and relative percentage for each fraction could be calculated as a function of extraction equilibrium pH. The soils were also analyzed for solid phase total organic carbon and total recoverable metals (EPA Method 3051). Partitioning coefficients were calculated for the metals and organic carbon (OC) based on solid phase concentrations (less the metal or OC removed by the extraction) divided by solution concentrations. Cu and Pb concentrations in solution as a function of extract equilibrium pH are greatest at low and high pH resulting in parabolic desorption/dissolution curves. While processes such as proton competition and proton promoted dissolution can account for high solution metal concentrations at low pH, these processes cannot account for higher Cu and Pb concentrations at high pH. DOC increases with increasing pH, concurrently with the increase in Cu and Pb solution concentrations. While the absolute concentrations of FA and HA generally increase with increasing pH, the relative proportional increase is greatest for HA . Variation in HA concentrations spans three orders of magnitude while FA concentrations vary an order of magnitude over the pH range examined. Correlation analysis strongly suggests that HA plays a major role in increasing the concentration of solution Cu and Pb with increasing pH in the 18 soils studied. The percentage of the OC that was due to FA was nearly constant over a wide pH range although the FA concentration increased with increasing pH and its concentration was greater than that of the HA fraction at lower pH values (pH = 3-5). Thus, in more acidic environments, FA may play a larger role than HA in governing organo-metallic interactions. For Cd, Ni, and Zn, the desorption/dissolution pattern shows high metal solution concentrations at low pH with slight increases in solution concentrations at extremely high pH values (pH>10). The results presented here suggest that the effects of dissolved organic carbon on the mobilization of Cd, Ni, and Zn may only occur in systems governed by very high pH. At high pH, it is difficult to distinguish in this study whether the slightly increased solution-phase concentrations of these cations is due to DOC or hydrolysis reactions. These high pH environments would rarely occur in natural settings.